EP1986596A1

EP1986596A1 - Skin-calming oxidative hair treatment

Info

Publication number: EP1986596A1
Application number: EP07703177A
Authority: EP
Inventors: Martina Seiler; Detlef Hollenberg; Thomas Döring
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-02-21
Filing date: 2007-02-01
Publication date: 2008-11-05
Also published as: WO2007096045A1; DE102006060944A1

Abstract

The skin is subjected to stress when using oxidative cosmetics. The cosmetic use of at least one representative of the group which is formed from compounds according to formula (I), in which R1 is a C2- to C12-acyl group and R2 is a C2- to C30-alkyl group, Theobroma cacao extract, compounds according to formula (II), in which R3 is a linear C12- to C30-alkyl group or a saturated or unsaturated ?-(C12- to C20)-acyloxy-(C12-C30)-alkyl group (such as, preferably, tricosanyl, heptadecanyl or ?-(octadeca-9,12-dienoyloxy)nonacosanyl) and R4 is a saturated or unsaturated C15-alkyl group or a saturated or unsaturated C15-hydroxyalkyl group (such as, for example, pentadeca-1-en-1-yl, 3-hydroxypentadeca-1-en-1-yl, 1-hydroxypentadecanyl), hydrolysed yeast extract, hydrolysed lupin protein, in particular from Lupinus albus, rosemary extract, Castanea sativa extract, Mentha piperita leaf extract, N-(C8- to C30)-acyl)-4-hydroxyproline (C8- to C30)-alkyl ester, cholesterol, compounds of the formula (III), in which R1, R2 and R3, independently of one another, are a hydrogen atom, -CH3, -CH2CH3, -CH(CH3)2, -CH2CH2CH3, -CH(CH3)CH2CH3, -CH2CH(CH3)2, -C(CH3)3, n is 1 or 2, linoleic acid, vitamin C and derivatives thereof and niacinamide offers the user of oxidative hair-treatment compositions the possibility of reducing this stress, calming the skin and in particular reducing skin dryness and itching. A corresponding method for calming skin and the compositions that can be used therein are likewise described.

Description

"Calming oxidative hair treatment"

The present invention relates to the cosmetic use of selected active ingredients for soothing the skin during or after the oxidative hair treatment, in particular for reducing the dryness of the skin and for reducing the itching. A corresponding method for calming the skin, as well as the agents which can be used therein, are likewise the subject matter of the present invention.

Human hair is today treated in a variety of ways with hair cosmetic preparations. These include, for example, the cleansing of hair with shampoos, the care and regeneration with rinses and cures and the bleaching, dyeing and shaping of the hair with dyes, tinting agents, waving agents and styling preparations.

In addition to hair, as part of the oxidative hair treatment, the skin is also exposed to an oxidant-containing cosmetic. The consumer should feel comfortable during and after the hair treatment and the skin and the skin feel of the consumer should not be affected by the oxidative hair treatment. However, some consumers feel a tightening of the skin or itching after an oxidative hair treatment. The skin reddens easily after an oxidative hair treatment or dries out a little or possibly tends to dandruff.

By dry skin and / or itching initiated scratching the accumulation of dander in the hair is increased. This side effect of the oxidative hair treatment leads to a cosmetically unacceptable result. It is therefore an object of the present invention to suppress possible skin-irritating side effects of cosmetics containing oxidizing agents as far as possible during the application and in particular to reduce the itching and dehydration of the skin.

It has now surprisingly been found that the object is achieved to a great extent by selected active ingredients of the agent of the first subject of the invention. The effect unfolds even during the oxidative hair treatment. A first subject of the present invention is therefore the cosmetic use of a composition comprising in a cosmetic carrier at least one active ingredient (W) selected from the group which is formed from compounds of the formula (I)

wherein

R ¹ is a C ₂ to C ₁₂ acyl group and

R ² is a C ₂ to C ₃₀ alkyl group,

Theobroma cacao extract,

Compounds according to formula (II),

wherein

R ³ is a linear C ₂ - to C ₃ o-alkyl group or a saturated or unsaturated ω-

(Ci ₂ - to C ₂ o) -acyloxy (Ci ₂ -C ₃₀ ) -alkyl group (as preferred tricosanyl, heptadecanyl or ω- (octadeca-9,12-dien-oyloxy) -nonacosanyl) and

R ⁴ is a saturated or unsaturated C ₅ -alkyl group or a saturated or unsaturated C ₁₅ -hydroxyalkyl group (such as, for example, pentadeca-1-en-1-yl, 3

Hydroxypentadeca-1-en-1-yl, 1-hydroxypentadecanyl), hydrolysed yeast extract, hydrolyzed lupine protein, in particular from Lupinus albus,

Rosemary extract,

Castanea sativa extract,

Mentha piperita leaf extract,

N- (C ₈ to C ₃₀ ) acyl) -4-hydroxyproline (C ₈ to C ₃₀ ) alkyl esters,

cholesterol,

Compounds of the formula (III) wherein

R ¹ , R ² and R ³ independently represent a hydrogen atom, -CH ₃ , -CH ₂ CH ₃ , -CH (CHs) ₂ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) _3> n is 1 or 2,

linoleic acid,

Vitamin C and derivatives thereof and

Niacinamide for soothing the skin, (in particular for reducing skin dryness and / or reducing itching) during or immediately after oxidative hair treatment.

As immediately after the oxidative hair treatment is understood in the context of the invention, an application that directly adjoins the oxidative hair treatment, wherein the oxidative cosmetic agent was previously rinsed from the hair and the hair is preferably still wet.

According to the invention, cosmetic creams, emulsions, gels or surfactant-containing foaming solutions, for example shampoos, foam aerosols or other preparations which are particularly suitable for use on the hair, are particularly suitable as cosmetic carriers. But it is also conceivable to integrate the ingredients in a powdered or tablet-like formulation, which is dissolved in water before use. The cosmetic carriers may in particular be aqueous or aqueous-alcoholic.

An aqueous cosmetic carrier contains at least 50% by weight of water.

For the purposes of the present invention, aqueous-alcoholic cosmetic carriers are to be understood as meaning aqueous solutions containing from 3 to 70% by weight of a C ₁ -C ₄ -alkyl alcohol, in particular ethanol or isopropanol. The compositions according to the invention may additionally contain further organic solvents, for example methoxybutanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol. Preference is given to all water-soluble organic solvents.

In the context of an oxidative hair treatment, the use of an oxidative cosmetic agent containing at least one oxidizing agent in a cosmetic carrier is defined according to the invention.

The oxidizing agents according to the invention are different from atmospheric oxygen and have such an oxidation potential that makes it possible to disulfide bridges within or between the To bind proteins of the hair keratin, to oxidatively lighten the natural color pigment melanin and / or to oxidize a developer-type oxidation dye precursor.

The oxidizing agent used is in particular hydrogen peroxide and / or at least one addition product thereof, in particular to inorganic or organic compounds, such as, for example, sodium perborate, sodium percarbonate, magnesium percarbonate,

Sodium percarbamide, polyvinylpyrrolidone n H ₂ O ₂ (n is a positive integer greater than 0), urea peroxide and melamine peroxide in question.

According to the invention, the oxidative cosmetic agent can also be applied to the hair together with a catalyst which activates the oxidation of the substrate, such as, for example, oxidation dye precursors or melanin. Such catalysts are e.g. Metal ions, iodides, quinones or certain enzymes.

Suitable metal ions are, for example, Zn ²⁺ , Cu ²⁺ , Fe ²⁺ , Fe ³⁺ , Mn ²⁺ , Mn ⁴⁺ , Li ⁺ , Mg ²⁺ , Ca ²⁺ and Al ³⁺ . Particularly suitable are Zn ²⁺ , Cu ²⁺ and Mn ²⁺ . The metal ions can in principle be used in the form of any physiologically acceptable salt or in the form of a complex compound. Preferred salts are the acetates, sulfates, halides, lactates and tartrates. By using these metal salts, both the formation of a color can be accelerated and the color shade can be specifically influenced.

Suitable enzymes are e.g. Peroxidases that can significantly increase the effect of small amounts of hydrogen peroxide. Furthermore, such enzymes are suitable according to the invention, which generate with the help of atmospheric oxygen in situ small amounts of hydrogen peroxide and activate biocatalytically in this way the oxidation of the dye precursors. Particularly suitable catalysts for the oxidation of dye precursors are the so-called 2-electron oxidoreductases in combination with the specific substrates, e.g. Pyranose oxidase and e.g. D-glucose or galactose,

Glucose oxidase and D-glucose, glycerol oxidase and glycerin,

Pyruvate oxidase and pyruvic acid or its salts, - alcohol oxidase and alcohol (MeOH, EtOH), lactate oxidase and lactic acid and its salts, tyrosinase oxidase and tyrosine, uricase and uric acid or their salts, choline oxidase and choline, amino acid oxidase and amino acids. The oxidizing agent is preferably in an amount of 1, 0 to 10 wt .-%, in particular from 3.0 to 10.0 wt .-%, each based on the weight of the ready-to-use agent, in the inventive composition.

In a simultaneous application of the oxidative cosmetic agent and the cosmetic agent of the invention, both agents may be mixed together, optionally immediately before use, or applied sequentially to the hair. In a preferred embodiment, the cosmetic agent used according to the invention therefore additionally contains at least one oxidizing agent.

The cosmetic agents used according to the invention contain the active compounds (W) according to the invention preferably in an amount of 0.01 to 7 wt .-%, particularly preferably from 0.1 to 5 wt .-%, each based on the weight of the ready-to-use agent.

The hydrolyzed yeast extract is particularly in the form of the raw material Relipidum Ref ^® (INCI name: Hydrolyzed Yeast Extract, Butylene Glycol, methyl parabens) of the company Coletica used in accordance with the invention used the means. An amount of 0.5 to 2.0% by weight of this raw material based on the weight of the ready-to-use cosmetic agent is preferred.

The hydrolyzed lupine protein, especially the protein of Lupinus Albus, is preferably in the form of the raw material Structurine ^® (INCI name: Hydrolyzed Lupine Protein (Lupinus Albus) from the company Silab used in the invention are used according to an amount of 2.0 to. 5.0% by weight of this raw material, based on the weight of the ready-to-use cosmetic agent, is preferred.

The rosemary extract is particularly in the form of the raw material Merospheres ^®: Company Barnet used (INCI name Rosmarinus Officinalis Extract, lecithin) in accordance with the invention used the means. An amount of 0.3 to 1.0% by weight of this raw material, based on the weight of the ready-to-use cosmetic agent, is preferred.

Castanea sativa extract is particularly in the form of the raw material Recoverine ^® (INCI name: Aqua (Water), Castanea sativa Extract) from the company Silab used in accordance with the invention used the means. An amount of 2.0 to 5.0% by weight of this raw material based on the weight of the ready-to-use cosmetic agent is preferred.

Mentha piperita Leaf the extract and the Theobroma cacao extract is in particular as a combination in the form of the raw material Caomint ^® (INCI name: Propylene Glycol, Aqua (Water), Mentha piperita (Peppermint) leaf extract, Theobroma cocoa (Cocoa) Extract) from Solabia in the compositions used in the invention. An amount of 1.0 to 3.0% by weight of this raw material, based on the weight of the ready-to-use cosmetic agent, is preferred.

The N- (C ₈ - to C ₃₀ ) -acyl) -4-hydroxyproline (C ₈ - to C ₃₀ ) -alkyl esters can be present both in the D and in the L form or as a mixture of both stereoisomers in particular as a racemate. As preferred representatives of N- (C ₈ - to C ₃₀ ) acyl) -4-hydroxy-L-proline (C ₈ - to C ₃₀ ) - alkyl esters, the Ci ₂ - are used to C ₂ o-alkyl esters, which in turn preferably carry a C ₁₂ - to C ₂ o-acyl group on the N atom. A particularly preferred ester is the N-hexadecanoyl-4-hydroxy-L-proline hexadecyl ester, which is marketed in particular by the company Symrise. An amount of from 0.1 to 1.0% by weight of this raw material, based on the weight of the ready-to-use cosmetic product, is preferred.

The compounds according to formula (I) have as derivatized dipeptide from tyrosine and arginine two stereochemical centers and can exist as S ₁ S, R ₁ R, R ₁ S and S, R isomers. Both radical R ¹ and R ² according to formula (I) can be derived from linear or branched, saturated or unsaturated hydrocarbon radicals. As preferred representatives of the compounds of the formula (I)

those compounds are used in which R ^{1 is} a C ₂ - to C ₈ acyl group and R ^{2 is} a Cur to C ₂₂ alkyl group. R ^{1 is} particularly preferably an acetyl group and R ^{2 is} a hexadecyl radical. The compounds of the formula (I) are preferably used in an amount of from 0.01 to 1.0% by weight, based on the weight of the ready-to-use cosmetic product. The compounds of formula I are in particular in the form of the raw material Calmosensine ^® of the company Sederma (INCI name: Dipeptide-1 cetyl ester Butylene Glycol, Aqua (Water), laureth 3, hydroxyethyl cellulose, acetyl) used in the present invention used the means. An amount of 1, 0 to 3.0 wt .-% of this raw material based on the weight of the ready-to-use cosmetic product is particularly preferred. According to the invention, the compounds ceramides I, ceramides II, ceramides 1, ceramides 2, ceramides 3, ceramides 5 and ceramides 6 known as INCI names are used as active compound (W) as preferred compounds according to formula II. Particular preference is given to using mixtures of the compounds of the formula (II) which are obtainable, for example, under the trade names SK-Influx® and Ceramide IM from the company Degussa Care Specialties, and the commercial product ceramides TIC-001, from the company Takasago International Corporation is marketed. The compounds of the formula (II) are preferably used in an amount of from 0.1 to 1.0% by weight, based on the weight of the ready-to-use cosmetic product.

Preferred compounds of the formula (III) are 2-ammonioethanesulfonate (taurine), 2- (N-methylammonio) ethanesulfonate, 2- (N, N-dimethylammonio) ethanesulfonate, 2- (N ₁ N ₁ N-

Trimethylammonio) ethanesulfonate, 3-aminopropane sulfonate (homotaurine), 3- (N-

Methylammonio) propanesulfonate, 3- (N, N-dimethylammonio) propanesulfonate, 3- (N ₁ N ₁ N-

Trimethylammonio) propane. Particularly preferred is 2-Ammonioethansulfonat.

A second aspect of the invention relates to cosmetic compositions comprising, in a cosmetic vehicle, a combination of at least one oxidizing agent and an active compound (W) selected from at least one member of the group which is formed from compounds of the formula (I)

wherein

R ¹ is a C ₂ to C ₁₂ acyl group and R ² is a C ₂ to C ₃₀ alkyl group, Theobroma Cacao extract, compounds of the formula (II),

R represents a linear C ₂ - to C ₃₀ alkyl group or a saturated or unsaturated ω- (C ₁₂ - to C ₂ o) acyloxy (C ₂ -C ₃ o) alkyl group (such as preferably tricosanyl, Heptadecanyl or ω - (octadeca-9,12-dienyloxy) -nonacosanyl) and

R ⁴ is a saturated or unsaturated C ₁₅ -alkyl group or a saturated or unsaturated C ₅ -hydroxyalkyl group (such as, for example, pentadeca-1-en-1-yl, 3-hydroxypentadeca-1-en-1-yl, 1-hydroxypentadecanyl) , hydrolysed yeast extract, hydrolyzed lupine protein, in particular from Lupinus Albus, rosemary extract, Castanea sativa extract, Mentha piperita leaf extract,

N- (C ₈ - to C ₃₀ ) -acyl) -4-hydroxyproline (C ₈ - to C ₃₀ ) -alkyl esters, cholesterol, - compounds of the formula (III),

in which R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, -CH ₃ , -CH ₂ CH ₃ ,

-CH (CH ₃ J ₂ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ J ₃ , n is 1 or 2,

linoleic acid,

Vitamin C and derivatives thereof and niacinamide.

The cosmetic agent according to the invention can be formulated as a rinse-off or leave-on product. It is inventively preferred to rinse the cosmetic agent after the exposure time of the keratin-containing fiber. It is inventively preferred to use the agent according to the invention in the context of a color change of the hair. For this purpose, the cosmetic compositions additionally contain at least one color-modifying component.

As oxidizing agents, the agents according to the invention preferably contain hydrogen peroxide and / or at least one addition product of hydrogen peroxide to inorganic or organic compounds.

The color-changing component is again preferably selected

(A) from at least one oxidation dye precursor of the type of developer components and optionally additionally at least one coupler component and / or

(b) from oxo dye precursors and / or

(c) from at least one direct dye and / or

(D) from at least one precursor of natural dyes and / or

(E) from at least one oxidizing agent and optionally additionally at least one bleach booster.

As developer components are usually primary aromatic amines with another, in the para or ortho position, free or substituted hydroxy or amino group, diaminopyridine, heterocyclic hydrazones, 4-aminopyrazole derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives used ,

It may be preferred according to the invention to use as the developer component a p-phenylenediamine derivative or one of its physiologically acceptable salts. Particular preference is given to p-phenylenediamine derivatives of the formula (Ent1)

) in which

G ¹ represents a hydrogen atom, a C ₁ - to C ₄ alkyl radical, a Ci to C ₄ - monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (d- to C ₄₎ alkoxy (d - to C ₄ ) -alkyl radical, a 4'-aminophenyl radical or a C 1 to C ₄ -alkyl radical which is substituted by a nitrogen-containing group, a phenyl or a 4'-aminophenyl radical;

G ² represents a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C ₄₎ alkoxy alkyl group (Cr to _C4), or a C ₁ - to C ₄ alkyl radical substituted with a nitrogenous group ;

G ³ represents a hydrogen atom, a halogen atom such as a chlorine, bromine, iodine or

Fluorine atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to

C ₄ -hydroxyalkyl radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to C ₄ -

Acetylaminoalkoxy radical, a C ₁ - to C ₄ -mesylaminoalkoxy radical or a C ₁ - to C ₄ -

Carbamoylaminoalkoxyrest;

G ⁴ represents a hydrogen atom, a halogen atom or a C ₁ - to C ₄ -alkyl radical or when G ³ and G ⁴ are ortho to each other, they may together form a bridging α, ω-alkylenedioxy group, such as, for example, an ethylenedioxy group.

Examples of the C 1 -C ₄ -alkyl radicals mentioned as substituents in the compounds according to the invention are the groups methyl, ethyl, propyl, isopropyl and butyl. Ethyl and methyl are preferred alkyl radicals. C ₁ -C ₄ -alkoxy radicals which are preferred according to the invention are, for example, a methoxy or an ethoxy group. Furthermore, as preferred examples of a C ₁ - to C ₄ -hydroxyalkyl group, a hydroxymethyl, a 2-hydroxyethyl, a 3-hydroxypropyl or a 4-hydroxybutyl group may be mentioned. A 2-hydroxyethyl group is particularly preferred. A particularly preferred C ₂ to C ₄ polyhydroxyalkyl group is the 1, 2-dihydroxyethyl group. Examples of halogen atoms are according to the invention F, Cl or Br atoms, Cl atoms are very particularly preferred. The other terms used are derived according to the invention from the definitions given here. Examples of nitrogen-containing groups of the formula (Ent1) are in particular the amino groups, C ₁ to C ₄ monoalkylamino groups, C ₁ to C ₄ dialkylamino groups, C ₁ to C ₄ trialkylammonium groups, C ₁ to C ₄ monohydroxyalkylamino groups, Imidazolinium and ammonium.

Particularly preferred p-phenylenediamines of the formula (Ent1) are selected from p-phenylenediamine, p-toluenediamine, 2-chloro-p-phenylenediamine, 2,3-dimethyl-p-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2 , 6-diethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N, N-dipropyl-p-phenylenediamine, 4-amino 3-methyl- (N, N-diethyl) -aniline, N, N-bis- (β-hydroxyethyl) -p-phenylenediamine, 4-N, N-bis- (β-hydroxyethyl) amino-2-methylaniline, 4-N, N-bis- (β-hydroxyethyl) amino-2-chloroaniline, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine, 2-fluoro-p - phenylenediamine, 2-isopropyl-p-phenylenediamine, N- (β-hydroxypropyl) -p-phenylenediamine, 2-hydroxymethyl-p-phenylenediamine, N, N-dimethyl-3-methyl-p-phenylenediamine, N, N- ( .beta.-ethyl, hydroxyethyl) -p-phenylenediamine, N- (β, γ-dihydroxypropyl) -p-phenylenediamine, N- (4'-aminophenyl) -p-phenylenediamine, N-phenyl-p-phenylenediamine, 2- (β-hydroxyethyloxy) - p-phenylenediamine, 2- (.beta.-acetylaminoethyloxy) -p-phenylenediamine, N- (.beta.-methoxyethyl) -p-phenylenediamine and 5,8-diaminobenzo-1, 4-dioxane and their physiologically acceptable salts.

Very particular preferred p-phenylenediamine derivatives of the formula (Ent1) according to the invention are p-phenylenediamine, p-toluenediamine, 2- (β-hydroxyethyl) -p-phenylenediamine, 2- (α, β-dihydroxyethyl) -p-phenylenediamine and N, N -bis- (SS-hydroxyethyl) -p-phenylenediamine.

It may further be preferred according to the invention to use as developer component compounds which contain at least two aromatic nuclei which are substituted by amino and / or hydroxyl groups.

Among the binuclear developer components that can be used in the compositions according to the invention, mention may be made in particular of the compounds which correspond to the following formula (Ent2) and their physiologically tolerated salts:

in which:

Z ¹ and Z ² independently of one another represent a hydroxyl or NH ₂ radical which is optionally substituted by a C ₁ - to C ₄ -alkyl radical, by a C ₁ - to C ₄ -hydroxyalkyl radical and / or by a bridge Y. or which is optionally part of a bridging ring system, the bridge Y is an alkylene group having 1 to 14 carbon atoms, such as a linear or branched alkylene chain or an alkylene ring, which is one or more nitrogen-containing groups and / or one or more heteroatoms such as oxygen , Sulfur or nitrogen atoms may be interrupted or terminated and may optionally be substituted by one or more hydroxyl or C ₁ - to C ₈ -alkoxy radicals, or a direct bond,

G ⁵ and G ⁶ independently of one another represent a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkyl radical, a C ₁ - to C ₄ -Aminoalkylrest or a direct connection to

Bridging Y,

G ⁷ , G ⁸ , G ⁹ , G ¹⁰ , G ¹¹ and G ¹² independently represent a hydrogen atom, a direct bond to the bridge Y or a C ₁ - to C ₄ -alkyl radical, with the provisos that the compounds of the formula (Ent2) contain only one bridge Y per molecule and the compounds of the formula (Ent2) contain at least one amino group which carries at least one hydrogen atom.

The substituents used in formula (Ent2) are inventively defined analogous to the above statements.

Preferred binuclear developer component of the formula (Ent2) are in particular: N, N'-bis (.beta.-hydroxyethyl) -N, N ^l bis (4'-aminophenyl) -1, 3-diamino-propan-2-ol _I N, N'-bis (β-hydroxyethyl) -N, N'-bis (4'-aminophenyl) ethylenediamine, N, N'-bis (4-aminophenyl) tetramethylenediamine, N ₁ N ¹ - Bis N, N'-bis (4-aminophenyl) tetramethylenediamine, N, N'-diethyl-N, N ' -bis (4 ^l -amino-3'-methylphenyl) -ethylenediamine, bis (2-hydroxy-5-aminophenyl) -methane, 1, 3-bis- (2,5-diaminophenoxy) -propan-2-ol , N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane, N, N'-bis (2-hydroxy-5-aminobenzyl) -piperazine, N- (4'-aminophenyl) -p -phenylenediamine and 1, 10-bis- (2 ', 5'-diarπinophenyl) -1, 4,7,10-tetraoxadecane and their physiologically acceptable salts.

Very particularly preferred double bases of formula (Ent2) are N ₁ N'-bis (.beta.-hydroxyethyl) -N, N'-bis- (4'-aminophenyl) -1, 3-diamino-propan-2-ol _l Bis (2-hydroxy-5-aminophenyl) methane, 1, 3-bis (2,5-diaminophenoxy) -propan-2-ol, N, N'-bis (4'-aminophenyl) -1, 4-diazacycloheptane and 1, 10-bis (2 ', 5'-diaminophenyl) -1, 4,7,10-tetraoxadecan or one of its physiologically acceptable salts.

Furthermore, it may be preferred according to the invention to use as the developer component a p-aminophenol derivative or one of its physiologically tolerable salts. Particular preference is given to p-aminophenol derivatives of the formula (Ent3)

in which: G ¹³ represents a hydrogen atom, a halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to

C ₄ -monohydroxyalkyl radical, a C ₂ - to C ₄ -polyhydroxyalkyl radical, a (C ₁ - to C ₄ ) -alkoxy radical

(C ₁ - to C ₄ ) -alkyl radical, a C ₁ - to C ₄ -aminoalkyl radical, a HyOrOXy- (C ₁ - to C ₄ ) -alkylamino radical, a C ₁ - to C ₄ -hydroxyalkoxy radical, a C ₁ - to

C ₄ ) -aminoalkyl or a (di-C ₁ - to Cj-AlkylaminoMC _T to C ₄ ) alkyl, and

G ¹⁴ is a hydrogen or halogen atom, a C ₁ - to C ₄ -alkyl radical, a C ₁ - to C ₄ -

Monohydroxyalkyl radical, a C ₂ - to C ₄ polyhydroxyalkyl radical, a (C ₁ - to C) -AIkOXy- -, alkyl (C ₁ to C ₄₎ a C ₁ - to C ₄ aminoalkyl radical or a C ₁ - to C _4- cyanoalkyl radical,

G ¹⁵ is hydrogen, C ₁ - to C ₄ -alkyl, C ₁ - to C ₄ -monohydroxyalkyl, C ₂ - to C ₄ -polyhydroxyalkyl, phenyl or benzyl, and

G ¹⁶ is hydrogen or a halogen atom.

The substituents used in formula (Ent3) are defined according to the invention analogously to the above statements.

Preferred p-aminophenols of the formula (Ent3) are, in particular, p-aminophenol, N-methyl-p-aminophenol, 4-amino-3-methylphenol, 4-amino-3-fluorophenol, 2-hydroxymethyl-amino-4-aminophenol, 4 -Amino-3-hydroxymethylphenol, 4-amino-2- (β-hydroxyethoxy) -phenol, 4-arnino-2-methylphenol, 4-amino-2-hydroxymethylphenol, 4-amino-2-methoxymethyl-phenol, 4-amino -2-aminomethylphenol, 4-amino-2- (β-hydroxyethyl-aminomethyl) phenol, 4-amino-2- (α, β-dihydroxyethyl) phenol, 4-amino-2-fluorophenol, 4-amino-2 -chlorophenol, 4-amino-2,6-dichlorophenol, 4-amino-2- (diethyl-aminomethyl) -phenol and their physiologically acceptable salts.

Very particularly preferred compounds of the formula (Ent3) are p-aminophenol, 4-amino-3-methylphenol, 4-amino-2-aminomethylphenol, 4-amino-2- (α, β-dihydroxyethyl) -phenol and 4-amino 2- (diethylaminomethyl) -phenol.

Further, the developer component may be selected from o-aminophenol and its derivatives such as 2-amino-4-methylphenol, 2-amino-5-methylphenol or 2-amino-4-chlorophenol.

Further, the developer component may be selected from heterocyclic developer components, such as the pyridine, pyrimidine, pyrazole, pyrazole pyrimidine derivatives and their physiologically acceptable salts.

Preferred pyridine derivatives are, in particular, the compounds described in the patents GB 1 026 978 and GB 1 153 196, such as 2,5-diamino-pyridine, 2- (4'-methoxyphenyl) amino 3-Amino-pyridine, 2,3-diamino-6-methoxy-pyridine, 2- (β-methoxyethyl) amino-3-amino-6-methoxy-pyridine and 3,4-diamino-pyridine.

Preferred pyrimidine derivatives are, in particular, the compounds described in German Patent DE 2 359 399, Japanese Laid-Open Patent Publication JP 02019576 A2 or in the published patent application WO 96/15765, such as 2,4,5,6-tetraaminopyrimidine, 4-hydroxy- 2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine ₁ 2-dimethylamino-4,5 ₁ 6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine and 2,5,6- triaminopyrimidine.

Preferred pyrazole derivatives are, in particular, the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969, WO 94/08970, EP-740 931 and DE 195 43 988, such as 4,5 Diamino-1-methylpyrazole, 4,5-diamino-1- (β-hydroxyethyl) pyrazole, 3,4-diaminopyrazole, 4,5-diamino-1- (4'-chlorobenzyl) pyrazole, 4.5- Diamino-1, 3-dimethylpyrazole, 4,5-diamino-3-methyl-1-phenylpyrazole, 4,5-diamino-1-methyl-3-phenylpyrazole, 4-amino-1,3-dimethyl-5-hydrazinopyrazole, 1-Benzyl-4,5-diamino-3-methylpyrazole, 4,5-diamino-3-tert-butyl-1-methylpyrazole, 4,5-diamino-1-tert-butyl-3-methylpyrazole, 4, 5-diamino-1- (β-hydroxyethyl) -3-methylpyrazole, 4,5-diamino-1-ethyl-3-methylpyrazole, 4,5-diamino-1-ethyl-3- (4'-methoxyphenyl) pyrazole , 4,5-diamino-1-ethyl-3-hydroxymethylpyrazole, 4,5-diamino-3-hydroxymethyl-1-methylpyrazole, 4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole, 4,5-diamino-3 methyl-1-isopropylpyrazole, 4-amino-5- (2-aminoethyl) amino-1,3-dimethylpyrazole, 3,4,5-

Triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole, 3,5-diamino-1-methyl-4-methylaminopyrazole and 3,5-diamino-4- (β-hydroxyethyl) amino-1-methylpyrazole.

Preferred pyrazolopyrimidine derivatives are, in particular, the derivatives of the pyrazolo [1,5-a] opyrimidine of the following formula (Ent4) and their tautomeric forms, if a tautomeric equilibrium exists:

in which:

G ¹⁷ , G ¹⁸ , G ¹⁹ and G ²⁰ independently of one another represent a hydrogen atom, a C ₁ - to C ₄ -alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl radical, a C ₂ - to C ₄ - Polyhydroxyalkylrest a (C ₁ - to C ₄ ) alkoxy (C _r to C ₄ ) alkyl, a C ₁ - to C ₄ - aminoalkyl, which may optionally be protected by an acetyl-ureide or a sulfonyl radical a (C ₁ - to C ₄₎ alkylamino (C _r to C ₄₎ alkyl a di - aminoalkyl (Ci to _C4), wherein the - [(C _r to C ₄₎ alkyl] Dialkyl radicals optionally one Form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ ) - [hydroxyalkyl] - (C ₁ - to CO -aminoalkyl radical, the X- radicals are each independently a hydrogen atom, a C ₁ - to C ₄ - alkyl radical, an aryl radical, a C ₁ - to C ₄ -hydroxyalkyl group, a C ₂ - to C ₄ - polyhydroxyalkyl radical, a Ci to C ₄ - Aminoalkyl radical, a (C ₁ to C ₄ ) alkylamino (C ₁ to C ₄ ) alkyl radical, a di-J (C ₁ to C ₄ ) alkyl] - (C ₁ to C ₄ ) aminoalkyl radical where the dialkyl radicals optionally form a carbon cycle or a heterocycle having 5 or 6 chain members, a C ₁ - to C ₄ -hydroxyalkyl or a di- (C ₁ - to C ₄ -hydroxyalkyl) aminoalkyl radical, an amino radical, a Ci - to C ₄ -alkyl or di (C ₁ - to C ₄ -hydroxyalkyl) amino, a halogen atom, a carboxylic acid group or a sulfonic acid group, i has the value 0, 1, 2 or 3, p has the value 0 or 1 , q has the value 0 or 1 and n has the value 0 or 1, with the proviso that the sum of p + q is not equal to 0, if p + q equals 2, n has the value 0, and the groups NG ¹⁷ G ¹⁸ and NG ¹⁹ G ²⁰ occupy the positions (2, 3); (5,6); (6,7); (3,5) or (3,7); wweennnn pp ++ qq gglleeiicchh 11 iisstt ,, nn ddeenn WWeerrtt 11 hhaatt ,, and dd the groups NG ¹⁷ G ¹⁸ (or NG ¹⁹ G ²⁰ ) and the

Group OH occupy the positions (2,3); (5,6); (6,7); (3,5) or (3,7);

The substituents used in formula (Ent4) are defined according to the invention analogously to the above statements.

When the pyrazolo [1,5-a] pyrimidine of the above formula (Ent4) contains a hydroxy group at one of the 2, 5 or 7 positions of the ring system, there is a tautomeric equilibrium which is shown, for example, in the following scheme:

Among the pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) may be mentioned in particular:

Pyrazolo [1,5-a] pyrimidine-3,7-diamine; 2,5-dimethyl-pyrazolo [1,5-a] pyrimidine-3,7-diamine;

Pyrazolo [1,5-a] pyrimidine-3,5-diamine;

2,7-dimethyl-pyrazolo [1.δ-alpyrimidin-S, S-diamine;

3-aminopyrazolo [1,5-a] pyrimidin-7-ol;

3-aminopyrazolo [1,5-a] pyrimidin-5-ol;

2- (3-aminopyrazolo [1,5-a] pyrimidin-7-ylamino) ethanol;

2- (7-aminopyrazolo [1,5-a] pyrimidin-3-ylamino) ethanol;

2 - [(3-aminopyrazolo [1,5-a] pyrimidin-7-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

2 - [(7-aminopyrazolo [1,5-a] pyrimidin-3-yl) - (2-hydroxy-ethyl) -amino] -ethanol;

5,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

2,6-dimethylpyrazolo [1,5-a] pyrimidine-3,7-diamine;

3-amino-7-dimethylamino-2,5-dimethylpyrazolo [1,5-a] pyrimidine; and their physiologically acceptable salts and their tautomeric forms when tautomeric equilibrium is present.

The pyrazolo [1, 5-a] pyrimidines of the above formula (Ent4) can be prepared as described in the literature by cyclization from an aminopyrazole or hydrazine.

As coupler components m-phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenol derivatives and heterocyclic compounds are generally used.

Preferred coupler components according to the invention are m-aminophenol and its derivatives, such as, for example, 5-amino-2-methylphenol, N-cyclopentyl-3-aminophenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2 6-Dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5- (2'- Hydroxyethyl) amino-2-methylphenol, 3- (diethylamino) -phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5- (methylamino) -benzene, 3-ethylamino-4-methylphenol and 2,4 Dichloro-3-aminophenol, o-aminophenol and its derivatives, m-diaminobenzene and its derivatives such as, for example, 2,4-diaminophenoxyethanol, 1,3-bis- (2 ', 4'-diaminophenoxy) -propane, 1- Methoxy-2-amino-4- (2'-hydroxyethylamino) benzene, 1,3-bis (2 ', 4'-diaminophenyl) -propane ₁ 2,6-bis (2'-hydroxyethylamino) -1-methylbenzene , 2 - ({3 - [(2-hydroxyethyl) amino] -4-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-

Hydroxyethyl) amino] -2-methoxy-5-methylphenyl} amino) ethanol, 2 - ({3 - [(2-

Hydroxyethyl) amino] -4,5-dimethylphenyl} amino) ethanol, 2- [3-morpholin-4- ylphenyl) amino] ethanol, 3-amino-4- (2-methoxyethoxy) -5-methylphenylamine and 1-amino-3-bis- (2'-hydroxyethyl) aminobenzene, o-diaminobenzene and its derivatives such as 3,4 Diaminobenzoic acid and 2,3-diamino-1-methylbenzene,

Di- or trihydroxybenzene derivatives such as resorcinol, resorcinol monomethyl ether, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, 2-chlororesorcinol, 4-chlororesorcinol, pyrogallol and 1,2,4-trihydroxybenzene, pyridine derivatives such as 2,6-dihydroxypyridine , 2-amino-3-hydroxypyridine, 2-amino-5-chloro-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine, 2,6-dihydroxy-3,4-dimethylpyridine, 2,6-dihydroxy 4-methylpyridine, 2,6-diaminopyridine, 2,3-diamino-6-methoxypyridine and 3,5-diamino-2,6-dimethoxypyridine,

Naphthalene derivatives such as 1-naphthol, 2-methyl-1-naphthol, 2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1 , 8-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and 2,3-dihydroxynaphthalene,

Morpholine derivatives such as 6-hydroxybenzomorpholine and 6-aminobenzomorpholine,

Quinoxaline derivatives such as 6-methyl-1,2,3,4-tetrahydroquinoxaline, pyrazole derivatives such as 1-phenyl-3-methylpyrazol-5-one, indole derivatives such as 4-hydroxyindole, 6-hydroxyindole and 7-hydroxyindole, pyrimidine derivatives such as For example, 4,6-diaminopyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2,4-diamino-6-hydroxypyrimidine, 2,4,6-trihydroxypyrimidine, 2-amino-4-methylpyrimidine, 2-amino-4-hydroxy 6-methylpyrimidine and 4,6-dihydroxy-2-methylpyrinnidine, or methylenedioxybenzene derivatives such as 1-hydroxy-3,4-methylenedioxybenzene, 1-amino-3,4-methylenedioxybenzene and 1 - (2'-hydroxyethyl) -amino 3,4-methylenedioxybenzene and their physiologically acceptable salts.

Particularly preferred coupler components according to the invention are 1-naphthol, 1, 5, 2,7- and 1, 7-dihydroxynaphthalene, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcinol , 2-chloro-6-methyl-3-aminophenol, 2-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol and 2,6-dihydroxy-3,4-dimethylpyridine and the physiologically acceptable salts of the aforementioned compounds.

The cosmetic agents contain the developer components preferably in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent.

The cosmetic compositions contain the coupler components preferably in an amount of 0.005 to 10 wt .-%, preferably from 0.1 to 5 wt .-%, each based on the total agent. The agent can be used as color-modifying component in the form of Oxofarbstoffvorprodukte at least one combination of at least one compound of the component

1 compounds containing a reactive carbonyl group with at least one compound of the component

2 compounds selected from (a) CH-acidic compounds, (b) compounds containing primary or secondary amino group or hydroxy group selected from primary or secondary aromatic amines, nitrogen-containing heterocyclic compounds and aromatic hydroxy compounds.

Compounds according to the invention having a reactive carbonyl group (also referred to below as reactive carbonyl compounds or component 1) have at least one carbonyl group as reactive group which reacts with the compounds of component 2 to form a chemical bond linking both components. Further, according to the invention, those compounds are also included as component 1 in which the reactive carbonyl group is derivatized or masked in such a way that the reactivity of the carbon atom of the derivatized or masked carbonyl group with respect to the component 2 is always present. These derivatives are preferably condensation compounds of reactive carbonyl compounds with a) amines and their derivatives to form imines or oximes as a condensation compound b) alcohols to form acetals or ketals as a condensation compound c) water to form hydrates as a condensation compound of aldehydes.

Component 1 is preferably selected from the group formed from acetophenone, propiophenone, 2-hydroxyacetophenone, 3-hydroxyacetophenone, 4-hydroxyacetophenone, 2-hydroxypropiophenone, 3-hydroxypropiophenone, 4-hydroxypropiophenone, 2-hydroxybutyrophenone, 3 Hydroxybutyrophenone, 4-hydroxybutyrophenone, 2,4-dihydroxyacetophenone, 2,5-dihydroxyacetophenone, 2,6-dihydroxyacetophenone, 2,3,4-trihydroxyacetophenone, 3,4,5-trihydroxyacetophenone, 2,4,6-dihydroxyacetophenone Trihydroxyacetophenone, 2,4,6-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone, 3,4,5-trimethoxyacetophenone diethyl ketal, 4-hydroxy-3-methoxy-acetophenone, 3,5-dimethoxy-4- hydroxyacetophenone, 4-aminoacetophenone, 4-dimethylaminoacetophenone, 4-morpholinoacetophenone, 4-piperidinoacetophenone, 4-imidazolinoacetophenone, 2-hydroxy-5-bromo-acetophenone, 4-hydroxy-3-nitroacetophenone, acetophenone-2-carboxylic acid, acetophenone-4 carboxylic acid, benzophenone, 4-

Hydroxybenzophenone, 2-aminobenzophenone, 4,4'-dihydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2-hydroxy-1-acetonaphthone, 1-hydroxybenzophenone 2-acetonaphthone, chromone, chromone-2-carboxylic acid, flavone, 3- Hydroxyflavone, 3,5,7-trihydroxyflavone, 4 ', 5,7-trihydroxyflavone, 5,6,7-trihydroxyflavone, quercetin, 1-indanone, 9-fluorenone, 3-hydroxyfluorenone, anthrone, 1, 8-dihydroxyanthrone, vanillin , Coniferylaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaldehyde, 2-ethoxybenzaldehyde, 3-ethoxybenzaldehyde, 4-ethoxybenzaldehyde, 4-hydroxy-2,3-dimethoxybenzaldehyde, 4-hydroxy-2,5-dimethoxybenzaldehyde , 4-hydroxy-2,6-dimethoxybenzaldehyde, 4-hydroxy-2-methylbenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-2,3-dimethylbenzaldehyde, 4-hydroxy-2 , 5-dimethylbenzaldehyde, 4-hydroxy-2,6-dimethylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 3,5-diethoxy-4 - hydroxybenzaldehyde, 2,6-diethoxy-4-hydroxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 2-hydroxy-4-methoxybenzaldehyde, 2-ethoxy-4-hydroxybenzaldehyde, 3-ethoxy 4-hydroxybenzaldehyde, 4-ethoxy-2-hydroxybenzaldehyde, 4-ethoxy-3-hydroxybenzaldehyde, 2,3-dimethoxybenzaldehyde, 2,4-dimeth oxybenzaldehyde, 2,5-dimethoxybenzaldehyde, 2,6-dimethoxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 2,3,4-trimethoxbenzaldehyde, 2,3,5-trimethoxybenzaldehyde, 2,3, 6-trimethoxybenzaldehyde, 2,4,6-trimethoxybenzaldehyde, 2,4,5-trimethoxybenzaldehyde, 2,5,6-trimethoxybenzaldehyde, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 2,6-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3,5-dihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 2,3,5-trihydroxybenzaldehyde, 2,3, 6-trihydroxybenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,5,6-trihydroxybenzaldehyde, 4-hydroxy-2-methoxybenzaldehyde, 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, 4-dimethylamino-2- hydroxybenzaldehyde, 4-diethylamino-2-hydroxybenzaldehyde, 4-pyrrolidinobenzaldehyde, A-

Morpholinobenzaldehyde, 2-morpholinobenzaldehyde, 4-piperidinobenzaldehyde, 2-methoxy-1-naphthaldehyde, 4-methoxy-1-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 2,4-dihydroxy-1-naphthaldehyde, 4-hydroxy-3- 3-hydroxy-4-methoxy-1-naphthaldehyde, 2,4-dimethoxy-1-naphthaldehyde, 3,4-dimethoxy-1-naphthaldehyde, 4-hydroxy-1-naphthaldehyde, 4-dimethylamino-1-naphthaldehyde, 2-methoxycinnamaldehyde, 4-methoxycinnamaldehyde, 4-hydroxy-3-methoxycinnamaldehyde, 3,5-dimethoxy-4-hydroxy-cinnamaldehyde, 4-dimethylaminocinnamaldehyde, 2-dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde, 4-dimethylamino-2-methylbenzaldehyde, 4-diethylamino-cinnamaldehyde, 4-dibutylaminobenzaldehyde, 4-diphenylaminobenzaldehyde, 4-dimethylamino-2-methoxybenzaldehyde dehyd, 4- (1-imidazolyl) -benzaldehyde, piperonal, 2,3,6,7-tetrahydro-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, 2,3,6,7-tetrahydro-8 -hydroxy-1H, 5H-benzo [ij] quinolizine-9-carboxaldehyde, N-ethylcarbazole-3-aldehyde, 2-formylmethylene-1,3,3-trimethylindoline (Fischer's aldehyde or tribasic aldehyde),

2-indolaldehyde, 3-indolaldehyde, 1-methylindole-3-aldehyde, 2-methylindole-3-aldehyde, 1-acetylindole-3-aldehyde, 3-acetylindole, 1-methyl-3-acetylindole, 2- (1 ' _l 3 ', 3'-trimethyl-2-indolinylidene) -acetaldehyde, 1-methylpyrrole-2-aldehyde, 1-methyl-2-acetylpyrrole, 4-pyridine aldehyde, 2-pyridine aldehyde, 3 Pyridine aldehyde, 4-acetylpyridine, 2-acetylpyridine, 3-acetylpyridine, pyridoxal, quinoline-3-aldehyde, quinoline-4-aldehyde, antipyrine-4-aldehyde, furfural, 5-nitrofurfural, 2-thenoyl-trifluoro-acetone, chromone 3-aldehyde, 3- (5'-nitro-2'-furyl) acrolein, 3- (2'-furyl) -acrolein and imidazole-2-aldehyde, 1, 3-diacetylbenzene, 1, 4-diacetylbenzene, 1 , 3,5-triacetylbenzene, 2-benzoyl-acetophenone, 2- (4'-methoxybenzoyl) -acetophenone, 2- (2'-furoyl) -acetophenone, 2- (2'-pyridoyl) -acetophenone and 2- (3 '- pyridoyl) acetophenone,

Benzylideneacetone, 4-hydroxybenzylideneacetone, 2-hydroxybenzylideneacetone, 4-methoxybenzylideneacetone, 4-hydroxy-3-methoxybenzylideneacetone, 4-dimethylaminobenzylideneacetone, 3,4-methylenedioxybenzylideneacetone, 4-pyrrolidinobenzylideneacetone, 4-piperidinobenzylideneacetone, 4-morpholinobenzylideneacetone, 4- Diethylaminobenzylideneacetone, 3-benzylidene-2,4-pentanedione, 3- (4'-hydroxybenzylidene) -2,4-pentanedione, 3- (4'-dimethylaminobenzylidene) -2,4-pentanedione, 2-benzylidenecyclohexanone, 2- (4 '-Hydroxybenzylidene) cyclohexanone, 2- (4'-dimethylaminobenzylidene) cyclohexanone, 2-benzylidene-1, 3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -1,3-cyclohexanedione, 3- ( 4'-dimethylaminobenzylidene) -1, 3-cyclohexanedione, 2-benzylidene-5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-hydroxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2 - (4'-hydroxy-3-methoxybenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2- (4'-dimethylaminobenzylidene) -5,5-dimethyl-1,3-cyclohexanedione, 2-benzylidenecyclopentanone , 2 '- (4-hydroxybenzylidene) -cyclopene tanon, 2- (4'-dimethylaminobenzylidene) cyclopentanone, 5- (4-dimethylaminophenyl) penta-2,4-dienal, 5- (4-diethylaminophenyl) penta-2,4-dienal, 5- (4-methoxyphenyl) penta-2,4-dienal, 5- (3,4-

Dimethoxyphenyl) penta-2,4-dienal, 5- (2,4-dimethoxyphenyl) penta-2,4-dienal, 5- (4-

Piperidinophenyl) penta-2,4-dienal, 5- (4-morpholinophenyl) -penta-2,4-dienal, 5- (4-

Pyrrolidinophenyl) penta-2,4-dienal, 6- (4-dimethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-diethylaminophenyl) hexa-3,5-dien-2-one, 6- (4-methoxyphenyl) hexa-3,5-dien-2-one, 6- (3,4-dimethoxyphenyl) hexa-3,5-dien-2-one, 6- (2,4-dimethoxyphenyl) hexa-3 , 5-dien-2-one, 6- (4-piperidinophenyl) hexa-3,5-dien-2-one, 6- (4-morpholinophenyl) hexa-3,5-dien-2-one, 6- ( 4

Pyrrolidinophenyl) hexa-3,5-dien-2-one, 5- (4-dimethylamino-1-naphthyl) penta-3,5-dienal, 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzaldehyde, 4-methyl-3 -nitrobenzaldehyde, 3-hydroxy-4-nitrobenzaldehyde, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-fluoro-3-nitrobenzaldehyde , 3-methoxy-2-nitrobenzaldehyde, 4-chloro-3-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde, 4-chloro-2-nitrobenzaldehyde, 2,4-dinitrobenzaldehyde, 2.6 Dinitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, 4,5-dimethoxy-2-nitrobenzaldehyde, 6-nitropiperonal, 2-nitropiperonal, 5-nitrovanillin, 2,5-dinitrosalicylaldehyde, 5-bromo-3-nitrosalicylaldehyde , 3-nitro-4-formylbenzenesulfonic acid, 4-nitro-1-naphthaldehyde, 2-nitrocinnamaldehyde, 3-nitrocinnamaldehyde, 4-nitrocinnamaldehyde, 9-methyl-3-carbazolaldehyde, 9-ethyl-3-carbazolaldehyde, 3-acetylcarbazole, 3 , 6-Diacetyl-9-ethylcarbazole, S-acetyl-θ-methylcarbazole, 1,4-dimethyl l-3-carbazolaldehyde, 1, 4,9-trimethyl-3-carbazolaldehyde, 4-formyl-1-methylpyridinium, 2-formyl-1-methylpyridinium, 4-formyl-1-ethylpyridinium, 2-formyl-i ethylpyridinium, 4-formyl-1-benzylpyridinium, 2-formyl-1-benzylpyridinium, 4-formyl-1,2-dimethylpyridinium, 4-formyl-1,3-dimethylpyridinium, 4-formyl 1-methylquinolinium, 2-formyl-1-methylquinolinium, 4-acetyl-1-methylpyridinium, 2-acetyl-1-methylpyridinium, 4-acetyl-1-methylquinolinium, 5-formyl-1-methyl-quinolinium, 6-formyl-1-methylquinolinium, 7-formyl-i-methylquinolinium, 8-formyl-1-methylquinolinium, 5-formyl-1-ethylquinolinium, 6-formyl-1-ethylquinolinium, 7-formyl-1-one ethylquinolinium, 8-formyl-1-ethylquinolinium, 5-formyl-1-benzylquinolinium, 6-formyl-1-benzylquinolinium, 7-formyl-1-benzylquinolinium, 8-formyl-1-benzylquinolinium, 5-formyl- i-allyl quinolinium, 6-formyl-1-allyl quinolinium, 7-formyl-i-allyl quinolinium and 8-formyl-i-allyl quinolinium, 5-acetyl-1-methyl quinolinium, θ-acetyl-i-methyl quinolinium, 7-acetyl-1-methylquinolinium, 8-acetyl-1-methylquinolinium, 5-acetyl-1-ethylquinolinium, 6-acetyl-1-ethylquinolinium, 7-acetyl-1-ethylquinolinium, 8-acetyl-1-one ethylquinolinium, 5-acetyl-1-benzylquinoline, 6-acetyl-1-benzylquinolinium, 7-acetyl-1-benzylquinolinium, 8-acetyl-1-benzylquin olinium, 5-acetyl-1-allyl-quinolinium, 6-acetyl-1-allyl-quinolinium, 7-acetyl-1-allyl-quinolinium and 8-acetyl-1-allyl-quinolinium, 9-formyl-1-methylacridinium, 4- (2 '-Formylvinyl) -1-nnethylpyridinium- _l 1, 3- dimethyl-2- (4'-formylphenyl) -benzimidazolium-, 1, 3-dimethyl-2- (4'-formylphenyl) -imidazolium-, 2- (4 '-Formylphenyl) -3-methylbenzothiazolium, 2- (4'-acetylphenyl) -3-methylbenzothiazolium, 2- (4'-formylphenyl) -3-methylbenzoxazolium, 2- (5'-formyl-2'-furyl ) -3-methylbenzothiazolium- ₁ 2- (5'-fomnyl-2'-furyl) -3-methylbenzothiazolium, 2- (5'-formyl-2'-thienyl) -3-methylbenzothiazolium, 2- (3 ' -Formylphenyl) -3-methylbenzothiazolium, 2- (4'-formyl-1-naphthyl) -3-methylbenzothiazolium, 5-chloro-2- (4'-formylphenyl) -3-methylbenzothiazolium, 2- (4 ' -Formylphenyl) -3,5-dimethylbenzothiazolium salts, preferably with benzenesulfonate, p-toluenesulfonate, methanesulfonate, perchlorate, sulfate, chloride, bromide, iodide, tetrachlorozincate, methylsulfate, trifluoromethanesulfonate or tetrafluoroborate as Gege ion, isatin, 1-methyl-isatin, 1-allyl-isatin, 1-hydroxymethyl-isatin, 5-chloro-isatin, 5-methoxy-isatin, 5-nitro-isatin, 6-nitro-isatin, 5-sulfo-isatin, 5-carboxyisatin, quinisatin, 1-methylquinisatin, and any mixtures of the above compounds.

As CH-acidic compounds are generally considered to carry a bound to an aliphatic carbon atom hydrogen atom, wherein due to electron-withdrawing substituents activation of the corresponding carbon-hydrogen bond is effected. According to the invention, CH-acidic compounds also include enamines which are formed by alkaline treatment of quaternized N-heterocycles with a CH-acidic alkyl group in conjugation with the quaternary nitrogen.

The CH-acidic compounds of component 2 are preferably selected from the group consisting of 1, 2,3,3-tetramethyl-3H-indolium iodide, 1, 2,3,3-tetramethyl-3H-indolium p-toluenesulfonate, 1, 2,3,3-tetramethyl-3H-indolium methanesulfonate, 1,3,3-trimethyl-2-methylenindoline (Fischer's base), 2,3-dimethylbenzothiazolium iodide, 2,3-dimethylbenzothiazolium p-toluenesulfonate, 2,3-dimethyl-naphtho [1,2-d] thiazolium p-toluenesulfonate, 3-ethyl-2-methylnaphtho [1,2-d] thiazolium p-toluenesulfonate, rhodanine, rhodanine-3-acetic acid, 1, 4-

Dimethylquinolinium iodide, 1, 2-dimethylquinolinium iodide, barbituric acid, thiobarbituric acid, 1, 3 Dimethylthiobarbituric acid, 1,3-diethylthiobarbituric acid, 1,3-diethylbarbituric acid, oxindole, 3-indoxylatoacetate, 2-coumaranone, 5-hydroxy-2-cumaranone, 6-hydroxy-2-cumaranone, 3-methyl-1-phenyl pyrazolin-5-one, indan-1, 2-dione, indan-1, 3-dione, indan-1-one, benzoylacetonitrile, 3-dicyanomethylenedan-1-one, 2-amino-4-imino-1, 3 thiazoline hydrochloride, 5,5-dimethylcyclohexane-1,3-dione, 2H-1,4-benzoxazin-4H-3-one, 3-ethyl-2-methylbenzoxazolium iodide, 3-ethyl-2-methylbenzothiazolium iodide, 1-ethyl-4-methyl-quinolinium iodide, 1-ethyl-2-methylquinolinium iodide, 1,3,3-trimethylquinoxaluminum iodide, 3-ethyl-2-methylbenzoxazolium p-toluenesulfonate, 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate, 1-ethyl-methyl-quinolinium p-toluenesulfonate, 1-ethyl-2-methyl-quinolinium p-toluenesulfonate, and 1,2,3-trichloro-quinoxalinium p-toluenesulfonate.

Preferred primary or secondary aromatic amines of component 2 are selected from N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, N- (2-hydroxyethyl) -N-ethyl-p-phenylenediamine, N, N-bis (2-hydroxyethyl) -p-phenylenediamine, N- (2-methoxyethyl) -p-phenylenediamine, 2,3-dichloro-p-phenylenediamine, 2,4-dichloro-p-phenylenediamine, 2.5- Dichloro-p-phenylenediamine, 2-chloro-p-phenylenediamine, 2,5-dihydroxy-4-morpholinoaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminomethyl-4-aminophenol, 2-hydroxymethyl-4- aminophenol, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,5-diaminotoluene, 2,5-diaminophenol, 2,5-diaminoanisole, 2,5, diaminophenethol, 4-amino-3-methylphenol, 2- 2,5-diaminophenyl) ethanol, 2,4-diaminophenoxyethanol, 2- (2,5-diaminophenoxy) ethanol, 3-amino-4- (2-hydroxyethyloxy) phenol, 3,4-methylenedioxyphenol, 3,4-methylenedioxyaniline, 3-amino-2,4-dichlorophenol, 4-methylaminophenol, 2-methyl-5-aminophenol, 3-methyl-4-aminophenol, 2-methyl-5- (2-hydroxyethyl) amino) phenol, 3-amino-2-chloro-6-methylphenol, 2-methyl-5-amino-4-chlorophenol, 5- (2-hydroxyethylamino) -4-methoxy-2-methylphenol, 4-amino-2- hydroxymethylphenol, 2-

(Diethylaminomethyl) -4-aminophenol, 4-amino-1-hydroxy-2- (2-hydroxyethylaminomethyl) benzene, 1-hydroxy-2-amino-5-methylbenzene, 1-hydroxy-2-amino-6- methylbenzene, 2-amino-5-acetamidophenol, 1, 3-dimethyl-2,5-diaminobenzene, 5- (3-hydroxypropylamino) -2-methylphenol, 5-amino-4-methoxy-2-methylphenol, N, N-dimethyl-3-aminophenol, N-cyclopentyl-3-aminophenol, 5-amino-4-fluoro-2-methylphenol, 2,4-diamino-5-fluorotoluene, 2,4-diamino-5- (2 -hydroxyethoxy) -toluene, 2,4-diamino-5-methylphenol, 3,5-diamino-2-methoxy-1-methylbenzene, 2-amino-4- (2-hydroxyethylamino) -anisole, 2,6-bis- (2-hydroxyethylamino) -1-methylbenzene, 1, 3-diamino-2,4-demethoxybenzene, 3,5-diamino-2-methoxy-toluene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2- Aminophenylacetic acid, 3-aminophenylacetic acid, 4-aminophenylacetic acid, 2,3-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,4-diaminobenzoic acid 3,5-diaminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 3 - amino 4-hydroxy-benzoic acid, 4-amino-3-hydroxy-benzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4-hydroxybenzenesulfonic acid, 4-amino-3-hydroxynaphthalene-1-sulfonic acid, 6- Amino-7-hydroxynaphthalene-2-sulfonic acid, 7-amino-4-hydroxynaphthalene-2-sulfonic acid, 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid, 3-amino-2-naphthoic acid, 3-aminophthalic acid, 5- Aminoisophthalic acid, 1, 3,5-triaminobenzene, 1, 2,4- Triaminobenzene, 1, 2,4,5-tetraaminobenzene, 2,4,5-triaminophenol, penta-aminobenzene, hexaaminobenzene, 2,4,6-triaminoresorcinol, 4,5-diaminobrencatechol, 4,6-diaminopyrogallol, 1- (2 - hydroxy-5-aminobenzyl) -2-imidazolidinone, 4-amino-2 - ((4 - [(5-amino-2-hydroxyphenyl) methyl] -piperazinyl) methyl) phenol, 3,5-diamino-4-hydroxy-catechol , 1,4-Bis- (4-aminophenyl) -1,4-diazacycloheptane, aromatic nitriles such as 2-amino-4-hydroxybenzonitrile, 4-amino-2-hydroxybenzonitrile, 4-aminobenzonitrile, 2,4-diaminobenzonitrile, nitro groups -containing amino compounds such as 3-amino-6-methylamino-2-nitro-pyridine, picramic acid, [8 - [(4-amino-2-nitrophenyl) -azo] -7-hydroxy-naphth-2-yl] -trimethylammonium chloride , [8 - ((4-amino-3-nitrophenyl) azo) -7-hydroxy-naphth-2-yl] -trimethylammonium chloride (Basic Brown 17), 1-hydroxy-2-amino-4,6-dinitrobenzene, 1-amino-2-nitro-4- [bis- (2-hydroxyethyl) amino] -benzene _l 1-amino-2 - [(2-hydroxyethyl) amino] -5-nitrobenzene (HC Yellow no. 5), 1 -Amino-2-nitro-4 - [(2-hydroxyethyl) amino] - b enol (HC Red No. 7), 2-chloro-5-nitro-N-2-hydroxyethyl-1,4-phenylenediamine, 1 - [(2-hydroxyethyl) amino] -2-nitro-4-aminobenzene ( HC Red No. 3), 4-amino-3-nitrophenol, 4-amino-2-nitrophenol, 6-nitro-o-toluidine, 1-amino-3-methyl-4 - [(2-hydroxyethyl) amino] - 6-nitrobenzene (HC Violet No. 1), 1-amino-2-nitro-4 - [(2,3-dihydroxypropyl) amino] -5-chlorobenzene (HC Red No. 10), 2- (4- Amino-2-nitroanilino) benzoic acid, 6-nitro-2,5-diaminopyridine, 2-amino-6-chloro-4-nitrophenol, 1-amino-2- (3-nitrophenylazo) -7-phenylazo-8-naphthol 3,6-disulphonic acid disodium salt (Acid blue No. 29), 1-amino-2- (2-hydroxy-4-nitrophenylazo) -8-naphthol-3,6-disulphonic acid disodium salt (Palatinchrome green), 1 amino 2- (3-chloro-2-hydroxy-5-nitrophenylazo) -8-naphthol-3,6-disulfonic acid disodium salt (gallium), 4-amino-4'-nitrostilbene-2,2'-disulfonic acid disodium salt, 2,4 Diamino-3 ', 5'-dinitro-2'-hydroxy-5-methyl-azobenzene (Mordant brown 4), 4'-amino-4-nitrodiphenylamine-2-sulfonic acid, 4'-amino-3'-nitrobenzophenone 2-carboxylic acid, 1-amino-4-nitro-2- (2-nitrobenzylideneamino) -benzene, 2- [2- (diethylamino) ethylamino] -5-nitroaniline, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid, 3 Amino-3'-nitrobiphenyl, 3-amino-4-nitro-acenaphthene, 2-amino-1-nitronaphthalene, 5-amino-6-nitrobenzo-1,3-dioxole, anilines, in particular nitro-group-containing anilines, such as 4 Nitroaniline, 2-nitroaniline, 1, 4-diamino-2-nitrobenzene, 1, 2-diamino-4-nitrobenzene, 1-amino-2-methyl-6-nitrobenzene, 4-nitro-1,3-phenylenediamine, 2 Nitro-4-amino-1- (2-hydroxyethylamino) -benzene, 2-nitro-1-amino-4- [bis (2-hydroxyethyl) amino] benzene, 4-amino-2-nitrodiphenylamine -2'-carboxylic acid, 1-amino-5-chloro-4- (2-hydroxyethylamino) -2-nitrobenzene, aromatic anilines or phenols having a further aromatic radical, as shown in the formula IV

in the • R ⁷ represents a hydroxy or an amino group by C ₄ alkyl, C _1-4 hydroxyalkyl, C _1-4 - alkoxy or C ^ alkoxy-C ^ alkyl groups may be substituted, .

• R ^8, R ^9, R ^10, R ¹¹ and R ¹² independently represent a hydrogen atom, a hydroxy or an amino group substituted with Ci-C ₄ alkyl, CVCj hydroxyalkyl, C ₁ -C ₄ -AIkOXy- , C ₁ -C ₄ - aminoalkyl or Ci-C ^ alkoxy-CrC _^ j alkyl groups may be substituted, stand, and

P is a direct bond, a saturated or unsaturated, optionally substituted by hydroxy groups carbon chain having 1 to 4 carbon atoms, a carbonyl, sulfoxy, sulfonyl or imino group, an oxygen or sulfur atom, or a group having the formula IVa

-Q '- (CH ₂ -Q-CH ₂ -Q ") _O - (IVa)

in the

Q signifies a direct bond, a CH ₂ or CHOH group,

• Q 'and Q "independently represent an oxygen atom, an NR ¹³ group, wherein R ^{13 represents} a hydrogen atom, a C _1-4 alkyl or a hydroxy-C _1-4 alkyl group, both of which together with the remainder of the molecule 5-, 6- or 7-membered ring, means the group O- (CH ₂ ) _P -NH or NH- (CH ₂ ) _P -O, wherein p and p 'are 2 or 3, and

O is a number from 1 to 4,

such as 4,4'-diaminostilbene and its hydrochloride, 4,4'-diaminostilbene-2,2'-disulphonic acid mono- or di-Na salt, 4-amino-4'-dimethylaminostilbene and its hydrochloride, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfoxide, 4,4'-diaminodiphenylamine, 4,4'-diaminodiphenylamine-2-sulfonic acid, 4,4'-diaminobenzophenone, 4,4 ' - Diaminodiphenylether, 3,3 ', 4,4'-tetraaminodiphenyl, 3,3', 4,4'-tetraamino-benzophenone, 1, 3-bis (2,4-diaminophenoxy) -propane, 1, 8-bis - (2,5-diaminophenoxy) -3,6-dioxaoctane, 1,3-bis (4-aminophenylamino) propane, 1,1,3-bis (4-aminophenylamino) -2-propanol, 1, 3 Bis- [N- (4-aminophenyl) -2-hydroxyethylamino] -2-propanol, N, N-bis [2- (4-aminophenoxy) ethyl] methylamine, N-phenyl-1,4-phenylenediamine and bis (5-amino-2-hydroxyphenyl) methane.

The abovementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, in particular as salts of inorganic acids, such as hydrochloric or sulfuric acid.

Suitable nitrogen-containing heterocyclic compounds are, for. B. 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-hydroxy-pyridine, 2,6-diamino-pyridine, 2,5-diamino-pyridine, 2- (aminoethylamino) -5-aminopyridine, 2,3-diamino-pyridine, 2-dimethylamino-5-amino-pyridine, 2-methylamino-3-amino-6-methoxy-pyridine, 2,3-diamino-6-methoxy-pyridine, 2,6- Dimethoxy-3,5-diamino-pyridine, 2,4,5-triamino-pyridine, 2,6-dihydroxy-3,4-dimethyl-pyridine, N- [2- (2,4-diaminophenyl) aminoethyl] -N- ( 5-amino-2-pyridyl) amine, N- [2- (4-aminophenyl) aminoethyl] -N- (5-amino-2-pyridyl) -amine, 2,4-dihydroxy-5,6-diaminopyrimidine _> 4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 2,4,5,6-tetraaminopyrimidine, 2-methylamino 4,5,6-triaminopyrimidine, 2,4-diaminopyrimidine, 4,5-diaminopyrimidine, 2-amino-4-methoxy-6-methylpyrimidine, 3,5-diaminopyrazole, SS-diamino-1,2,3-triazole, 3-aminopyrazole, 3-amino-5-hydroxypyrazole, 1-phenyl-4,5-diaminopyrazole, 1- (2-hydroxyethyl) -4,5-diaminopyrazole, 1-phenyl-3-methyl-4,5-diaminopyrazole, 4-Amino-2,3-dimethyl-1-phenyl-3-pyrazolin-5-one (4-aminoantipyrine), 1-phenyl-3-methylpyrazol-5-one, 2-aminoquinoline, 3-aminoquinoline, 8-amino - quinoline, 4-aminoquinaldine, 2-aminonicotinic acid, 6-aminonicotinic acid, 5-aminoisoquinoline, 5-aminoindazole, 6-aminoindazole, 5-aminobenzimidazole, 7-aminobenzene midazol, 5-aminobenzothiazole, 7-aminobenzothiazole, 2,5-dihydroxy-4-morpholino-aniline and indole and indoline derivatives such as 4-aminoindole, 5-aminoindole, 6-aminoindole, 7-aminoindole, 5, 6-dihydroxyindole, 5,6-dihydroxyindoline and 4-hydroxyindoline. Furthermore, as heterocyclic compounds according to the invention can be used in DE-U1-299 08 573 disclosed hydroxypyrimidines. The aforementioned compounds can be used both in free form and in the form of their physiologically acceptable salts, for. B. as salts of inorganic acids, such as hydrochloric or sulfuric acid, are used.

Suitable aromatic hydroxy compounds are, for. 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2,5-dimethylresorcinol, resorcinol, 3-methoxyphenol, pyrocatechol, hydroquinone, pyrogallol, phloroglucinol, hydroxyhydroquinone, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 3 Dimethylaminophenol, 2- (2-hydroxyethyl) phenol, 3,4-methylenedioxyphenol, 2,4-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 2,4-dihydroxy-phenylacetic acid, 3,4-dihydroxyphenylacetic acid, gallic acid, 2,4 , 6-trihydroxybenzoic acid, 2,4,6-trihydroxyace- tophenone, 2-chlororesorcinol, 4-chlororesorcinol, 1-naphthol, 1, 5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 6-dimethylamino-4 -hydroxy-2-naphthalenesulfonic acid and 3,6-dihydroxy-2,7-naphthalenesulfonic acid.

The compounds of component 1 and the compounds of component 2 are preferably used in the cosmetic compositions in each case in an amount of 0.03 to 65 mmol, in particular from 1 to 40 mmol, based on 100 g of the total Nuanciermittels used. The molar ratio of the compound of component 1 and the compound of component 2 may range from 0.5 to 2.0, preferably using equimolar amounts. The ready-to-use agent is prepared by separate mixing of components 1 and 2 immediately prior to application.

As precursors of naturally-analogous dyes such indoles and indolines are preferably used as the oxidation dye precursor of the developer type, the at least one hydroxy or Amino group, preferably as a substituent on the six-membered ring, have. These groups may carry further substituents, e.g. Example in the form of etherification or esterification of the hydroxy group or alkylation of the amino group. In a second preferred embodiment, the colorants contain at least one indole and / or indoline derivative.

Particularly suitable precursors of naturally-analogous hair dyes are derivatives of 5,6-dihydroxyindoline of the formula (Va),

in the independently of each other

R ¹ is hydrogen, a Ci-C ₄ alkyl group or a CVCVHydroxy-alkyl group, R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation, R ³ is hydrogen or a C 1 -C ₄ -alkyl group,

R ⁴ is hydrogen, a C _r C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ -AlkVIgOiPPe, and R ⁵ is one of the groups mentioned under R ⁴ , and physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indoline are 5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline,

N-butyl-5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid and 6-hydroxyindoline, 6-aminoindoline and 4-aminoindoline.

Particularly noteworthy within this group are N-methyl-5,6-dihydroxyindoline, N-ethyl-5,6-dihydroxyindoline, N-propyl-5,6-dihydroxyindoline, N-butyl-5,6-dihydroxyindoline and especially 5, 6-Dihydroxyindolin.

Also suitable as precursors of naturally-analogous hair dyes are derivatives of the 5,6-dihydroxyindole of the formula (Vb), in the independently of each other

R ¹ is hydrogen, a C ¹ -C ₄ -alkyl group or a C ¹ -C ₄ -hydroxyalkyl group,

R ² is hydrogen or a -COOH group, wherein the -COOH group may also be present as a salt with a physiologically compatible cation,

R ³ is hydrogen or a C 1 -C ₄ -alkyl group,

R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or a group -CO-R ⁶ , in which R ⁶ is a C ₁ -C ₄ alkyl group, and

R ⁵ is one of the groups mentioned under R ⁴ , as well as physiologically acceptable salts of these compounds with an organic or inorganic acid.

Particularly preferred derivatives of indole are 5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6- dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, 6-hydroxyindole, 6-aminoindole and 4-aminoindole.

Emphasized within this group are N-methyl-5,6-dihydroxyindole, N-ethyl-5,6-dihydroxyindole, N-propyl-5,6-dihydroxyindole, N-butyl-5,6-dihydroxyindole, and especially the 5,6 -Dihydroxyindol.

Preferred substantive dyes which are used in the cosmetic compositions as color-modifying component are nitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinones or indophenols. Preferred substantive dyes are those having the international designations or trade names HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, Acid Yellow 1, Acid Yellow 10, Acid Yellow 23, Acid Yellow 36, HC Orange Disperse Orange 3, Acid Orange 7, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, Acid Red 33, Acid Red 52, HC Red BN, Pigment Red 57: 1, HC Blue 2, HC Blue 12, Disperse Blue 3, Acid Blue 7, Acid Green 50, HC Violet 1, Disperse Violet 1, Disperse Violet 4, Acid Violet 43, Disperse Black 9, Acid Black 1, and Acid Black 52 known compounds as well as 1 , 4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol, 1, 4-bis (β-hydroxyethyl) amino-2-nitrobenzene, 3-nitro-4- (β-hydroxyethyl) aminophenol, 2- ( 2'-hydroxyethyl) amino-4,6-dinitrophenol, 1 - (Z-hydroxyethyl) amino-4-methyl-2-nitrobenzene, 1-amino-4- (2'-hydroxyethyl) amino-5-chloro-2 nitrobenzene, 4-amino-3-nitrophenol, 1- (2'-ureidoethyl) amino-4-nitrobenzene, 4-amino-2-nitrodiphenylamine-2'-carbon acid, 6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone, Picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid and 2-chloro-6-ethylamino-1-hydroxy-4-nitrobenzene.

Further, the cosmetic agents may contain a cationic substantive dye. Particularly preferred are

(a) cationic triphenylrimethane dyes such as Basic Blue 7, Basic Blue 26, Basic Violet 2 and Basic Violet 14,

(b) aromatic systems substituted with a quaternary nitrogen group, such as Basic Yellow 57, Basic Red 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well as

(c) substantive dyes containing a heterocycle having at least one quaternary nitrogen atom, as mentioned, for example, in EP-A2-998 908, which is incorporated herein by reference, in claims 6 to 11.

Preferred cationic substantive dyes of group (c) are in particular the following compounds:

CH ₃ SO ₄ ^"

The compounds of the formulas (DZ1), (DZ3) and (DZ5), which are also known by the names Basic Yellow 87, Basic Orange 31 and Basic Red 51, are very particularly preferred cationic substantive dyes of group (c).

The cationic direct dyes, which are sold under the trademark Arianor ^® are, according to the invention also very particularly preferred cationic direct dyes.

The cosmetic compositions contain the substantive dyes preferably in an amount of 0.01 to 20 wt .-%, based on the application ready means.

Furthermore, the cosmetic compositions according to the invention may also naturally occurring dyes such as henna red, henna neutral, henna black, chamomile flower, sandalwood, black tea, buckthorn bark, sage, bluewood, madder root, catechu, seder and alkano root are included.

It is not necessary for the oxidation dye precursors or the direct dyes to be in each case homogeneous compounds. Rather, in the cosmetic products, due to the production processes for the individual dyes, minor amounts of other components may be included, as far as they do not adversely affect the dyeing result or for other reasons, e.g. toxicological, must be excluded.

With regard to further optional components as well as the amounts of these components used, reference is expressly made to the relevant manuals known to the person skilled in the art, eg. B. Kh. Schrader, bases and formulations of cosmetics, 2nd edition, Hüthig book publisher, Heidelberg, 1989, referenced.

The actual oxidative colorant is prepared by separate storage of the dye precursors and the oxidizing agent immediately before use by mixing. In a preferred embodiment, the cosmetic agent is therefore mixed before application from a composition comprising at least one color-modifying component in a cosmetic carrier and a further composition containing at least one oxidizing agent in a cosmetic carrier.

In an application of oxidizing agents, the ready-to-use composition is conveniently prepared immediately prior to use by mixing a composition containing the oxidizing agent with the composition containing the color-modifying ones Components, manufactured. The resulting ready-to-use hair preparation should preferably have a pH in the range from 6 to 12, in particular from pH 7.5 to 10.

For a color change by means of brightening or bleaching of the hair, in addition to the oxidizing agents, at least one bleaching booster is preferably used in the cosmetic compositions according to the invention.

Bleach boosters are preferably used in bleaching agents for increasing the bleaching action of the oxidizing agent, in particular the hydrogen peroxide.

As bleach amplifiers, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylene diamines, in particular tetraacetylethylenediamine (TAED), _1- acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU) ₁ N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- diacetoxy-2,5-dihydrofuran.

As bleach booster, carbonate salts or bicarbonate salts can preferably be used according to the invention. These are preferably selected from the group of ammonium, alkali (especially sodium and potassium), and alkaline earth (especially calcium), carbonate salts or bicarbonate salts. Particularly preferred carbonate or bicarbonate salts are ammonium bicarbonate, ammonium carbonate,

Sodium bicarbonate, disodium carbonate, potassium bicarbonate, dipotassium carbonate and calcium carbonate. These particularly preferred salts can be used alone or in their mixtures of at least two representatives as bleaching amplifiers.

As bleach booster of the type of monoalkyl carbonates and their derivatives, at least one carbonic acid monoester and / or at least one carbonic acid monoamide are preferably used in the process according to the invention. Preferred carbonic acid monoesters are the carbonic acid monoesters of the formula (VI)

R-O-C-O-H (VI)

Il in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (VI), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably R is a Ci. _6- alkyl group. Examples of IVCe-alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Compositions particularly preferably used according to the invention are characterized in that the radical R in formula (VI) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl - As well as hydroxymethyl and hydroxyethyl radicals.

As an alternative to the carbonic acid monoester or in conjunction with it, carbonic acid monoamides can be used as bleach boosters in the anhydrous compositions. In this case, it is preferred according to the invention to use at least one carbonic acid monoamide of the formula (VII)

R-NH-C-O-H (VII)

Il o in which R is a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (VII), R preferably represents a substituted or unsubstituted, straight-chain or branched alkyl, alkenyl or alkynyl radical, preference being given to hydroxy, amino, nitro, sulfonic acid groups or halogens as substituents. Further preferred radicals R are phenyl and benzyl radicals and further substituted representatives. More preferably R is a Ci. _6- alkyl group. Examples of C ₁ -C ₆ -alkyl groups according to the invention are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl and hexyl.

Particularly preferred bleach boosters according to the invention of the formula (VII) are characterized in that the radical R in formula (VII) is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl , tert-butyl and hydroxymethyl and hydroxyethyl radicals. The acidic H atom of the carbonic acid monoester or monoamide can also be present in neutralized form, ie according to the invention it is also possible to use salts of carbonic acid monoesters or carbonic acid monoamides. Carbonic acid monoesters or the carbonic acid monoamides which are present in completely or partially neutralized form, preferably in the form of the alkali metal, ammonium, alkaline earth metal or aluminum salt and in particular in the form of its sodium salt, are preferred according to the invention.

As bleach boosters of the type of silyl carbonates and derivatives thereof, at least one silyl carbonate and / or at least one silyl carbamate are preferably incorporated into the compositions according to the invention. Preference is given to using silyl carbonates of the formula (VIII)

R ²

R ¹ -Si-OCOR ⁴ (VIII)

R ³ O

in which the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radical R ^{4 is} a chemical bond to the Si atom or one of the radicals R ¹ , R ² or R ³ , is a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or Aluminylgruppe or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (VIII) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among these, the alkyl radicals having 1 to 5 carbon atoms and the hydroxyalkyl radicals are preferred, so that preferred anhydrous compositions according to the invention are characterized in that the radicals R ¹ , R ² and R ³ in formula (VIII) are selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, fert-butyl, hydroxymethyl and hydroxyethyl radicals. Preferred radicals R ⁴ in the abovementioned formula (VIII) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

As bleach booster, at least one silyl carbamate of the formula (IX) may be present in the anhydrous composition according to the invention,

R ²

R ¹ -Si-OC-NR ⁴ R ⁵ (IX)

R ³ O

where the radicals R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, a saturated or unsaturated, straight-chain, branched or cyclic, substituted or unsubstituted hydrocarbon radical or a trialkylsilyl group, preferably a trimethylsilyl group or a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocycle or a halogen, a substituted or unsubstituted hydroxy, oxo, amino groups and the radicals R ⁴ and R ⁵ independently of one another for a chemical bond to the Si atom or to one of the radicals R ¹ , R ² or R ³ , a hydrogen atom, a saturated or unsaturated, straight-chain, branched, or cyclic, substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted SiIyI or alumino group or a substituted or unsubstituted aryl group or a substituted or unsub substituted heterocycle.

Preferred radicals R ¹ , R ² and R ³ in the abovementioned formula (IX) are substituted or unsubstituted, straight-chain or branched alkyl radicals. Among them, the alkyl groups having 1 to 5 carbon atoms and the hydroxyalkyl groups are preferred, so that compositions preferably used are characterized in that the groups R ¹ , R ² and R ³ in formula (IX) are selected from methyl, ethyl, n Propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, hydroxymethyl and hydroxyethyl radicals.

Preferred radicals R ⁴ and R ⁵ in the abovementioned formula (IX) are hydrogen, substituted or unsubstituted, straight-chain or branched alkyl radicals and trialkylsilyl radicals. Among them, preferred are hydrogen, methyl, ethyl, tert-butyl and trimethylsilyl radicals.

As further additional bleach boosters, in the compositions according to the invention preferably at least one compound selected from acetic acid, lactic acid, tartaric acid, citric acid, salicylic acid and ortho-phthalic acid may be contained. Bleach amplifiers are preferably peroxo compounds. Among the bleach-enhancing peroxy compounds according to the invention there are no addition products of hydrogen peroxide to other components and also not hydrogen peroxide itself. Moreover, the choice of peroxo compounds is subject to no restrictions. Preferred peroxy compounds are peroxydisulfate salts, persulfate salts, (especially ammonium peroxydisulfate, potassium peroxodisulfate, sodium peroxodisulfate, ammonium persulfate, potassium persulfate, sodium persulfate, potassium peroxydiphosphate) and peroxides (such as barium peroxide and magnesium peroxide). Among these peroxo compounds, which can also be used in combination, the inorganic compounds are preferred according to the invention. Particularly preferred are the peroxide isulfate, in particular ammonium peroxydisulfate.

The bleach boosters are contained in the cosmetic compositions preferably in amounts of 5-30 wt .-%, in particular in amounts of 8-20 wt .-%.

The cosmetic compositions, when acting as a bleaching agent, contain as preferred alkalizing agent at least one compound selected from ammonium, alkali metal and alkaline earth metal hydroxides, carbonates, bicarbonates, hydroxycarboxylates, metasilicates and carbamides, as well as alkali phosphates.

The cosmetic agents used in the process according to the invention may furthermore contain all active substances, additives and auxiliaries known for such preparations:

The washing with a shampoo is eliminated if a strong surfactant-containing carrier was used.

In many cases, the agents contain at least one surfactant, wherein in principle both anionic and zwitterionic, ampholytic, nonionic and cationic surfactants are suitable. In many cases, however, it has proved to be advantageous to select the surfactants from anionic, zwitterionic or nonionic surfactants.

Suitable anionic surfactants in the cosmetic compositions are all anionic surfactants suitable for use on the human body. These are characterized by a water-solubilizing, anionic group such. Example, a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 10 to 22 C-men men. In addition, glycol or polyglycol ether groups, ester, ether and amide groups and hydroxyl groups may be present in the molecule. Examples of suitable anionic surfactants are, in each case in the form of the sodium, potassium and ammonium as well as mono-, di- and trialkanol ammonium salts with 2 or 3 C atoms in the alkanol group, linear fatty acids having 10 to 22 C atoms (Soap), Ethercarbonsäuren the formula RO- (CH ₂ -CH ₂ O) _x -CH ₂ -COOH, in which R is a linear alkyl group having 10 to 22 carbon atoms and x = O or 1 to 16, acylsarcosides having 10 to 18 C Atoms in the acyl group, acyltaurides having 10 to 18 C atoms in the acyl group, acyl isethionates having 10 to 18 C atoms in the acyl group,

Sulfobernsteinsäuremono- and dialkyl esters having 8 to 18 carbon atoms in the alkyl group and sulfosuccinic monoalkylpolyoxyethylester having 8 to 18 carbon atoms in the alkyl group and 1 to 6 oxyethyl groups, linear alkanesulfonates having 12 to 18 carbon atoms, linear alpha-olefinsulfonates with 12 to 18 carbon atoms, alpha-sulfofatty acid methyl esters of fatty acids having 12 to 18 carbon atoms, alkyl sulfates and Alkylpolyglykolethersulfate the formula RO (CH ₂ -CH ₂ O) _x -SO ₃ H, in the R is a preferably linear alkyl group with 10 bis 18 C-atoms and x = 0 or 1 to 12, mixtures of surface-active hydroxysulfonates according to DE-A-37 25 030, sulfated hydroxyalkylpolyethylene and / or hydroxyalkylene-propylene glycol ethers according to DE-A-37 23 354,

Sulfonates of unsaturated fatty acids having 12 to 24 carbon atoms and 1 to 6 double bonds according to DE-A-39 26 344,

Esters of tartaric acid and citric acid with alcohols which are adducts of about 2-15 molecules of ethylene oxide and / or propylene oxide with fatty alcohols having 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule and in particular salts of saturated and in particular unsaturated C ₈ -C ₂₂ carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid ,

Nonionic surfactants contain as hydrophilic group z. A polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups. Such compounds are, for example

Addition products of 2 to 30 moles of ethylene oxide and / or 0 to 5 moles of propylene oxide to linear fatty alcohols having 8 to 22 carbon atoms, to fatty acids having 12 to 22 carbon atoms and on

Alkylphenols having 8 to 15 C atoms in the alkyl group,

C ₁₂ -C ₂₂ fatty acid mono- and diesters of addition products of 1 to 30 mol

Ethylene oxide with glycerine,

C ₈ -C ₂₂ alkyl mono- and oligoglycosides and their ethoxylated analogs and

Addition products of 5 to 60 moles of ethylene oxide with castor oil and hydrogenated castor oil. Preferred nonionic surfactants are alkyl polyglycosides of the general formula R ¹ O- (Z) _x . These connections are identified by the following parameters.

The alkyl radical R ¹ contains 6 to 22 carbon atoms and may be both linear and branched. Preference is given to primary linear and methyl-branched in the 2-position aliphatic radicals. Such alkyl radicals are, for example, 1-octyl, 1-decyl, 1-lauryl, 1-myristyl, 1-cetyl and 1-stearyl. Particularly preferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When using so-called "oxo-alcohols" as starting materials, compounds with an odd number of carbon atoms in the alkyl chain predominate.

The alkyl polyglycosides which can be used according to the invention can contain, for example, only one particular alkyl radical R ¹ . Usually, however, these compounds are prepared starting from natural fats and oils or mineral oils. In this case, the alkyl radicals R are mixtures corresponding to the starting compounds or corresponding to the particular work-up of these compounds.

Particular preference is given to those alkyl polyglycosides in which R ¹ consists essentially of C ₈ and C ₁₀ -alkyl groups, essentially of C ₁₂ and C ₁₄ -alkyl groups, essentially of C ₈ - to C- | ₆ alkyl groups or consisting essentially of Ci ₂ - to C ₁₆ alkyl groups.

As sugar building block Z it is possible to use any desired mono- or oligosaccharides. Usually, sugars with 5 or 6 carbon atoms and the corresponding oligosaccharides are used. Such sugars are, for example, glucose, fructose, galactose, arabinose, ribose, xylose, lyxose, allose, altrose, mannose, gulose, idose, talose and sucrose. Preferred sugar building blocks are glucose, fructose, galactose, arabinose and sucrose; Glucose is particularly preferred.

The alkyl polyglycosides which can be used according to the invention contain on average from 1.1 to 5 sugar units. Alkyl polyglycosides having x values of 1.1 to 1.6 are preferred. Very particular preference is given to alkyl glycosides in which x is 1: 1 to 1, 4.

In addition to their surfactant action, the alkyl glycosides can also serve to improve the fixation of fragrance components on the hair. The person skilled in the art will therefore prefer to use this substance class as a further constituent of the preparations according to the invention in the event that an effect of the perfume oil on the hair which exceeds the duration of the hair treatment is desired. The alkoxylated homologs of said alkyl polyglycosides can also be used according to the invention. These homologs may contain on average up to 10 ethylene oxide and / or propylene oxide units per alkyl glycoside unit.

Furthermore, zwitterionic surfactants can be used, in particular as cosurfactants. Zwitterionic surfactants are surface-active compounds which carry at least one quaternary ammonium group and at least one -COO ^M or -SO ₃ '^" group in the molecule. Particularly suitable zwitterionic surfactants are the so-called betaines such as N-alkyl-N, N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N, N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxylmethyl-3-hydroxyethyl imidazolines having in each case 8 to 18 C atoms in the alkyl or acyl group and the coco acylaminoethylhydroxyethylcarboxymethylglycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the INCI name Cocamidopropyl Betaine.

Also particularly suitable as co-surfactants are ampholytic surfactants. Ampholytic surfactants are to be understood as meaning those surface-active compounds which, apart from a C ₈ -C ₁₈ -alkyl or acyl group in the molecule, contain at least one free amino group and at least one -COOH or -SO ₃ H group and which are capable of forming internal salts are. Examples of suitable ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids each having about 8 to 18 C atoms in the alkyl group. Particularly preferred ampholytic surfactants are N-cocoalkylaminopropionate, cocoacylaminoethyl aminopropionate and C ₁₂ - _I8 - sarcosine.

According to the invention, the cationic surfactants used are, in particular, those of the quaternary ammonium compound type, the esterquats and the amidoamines.

Preferred quaternary ammonium compounds are ammonium halides, especially chlorides and bromides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. For example, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride, as well as the imidazolium compounds known under the INCI names Quaternium-27 and Quaternium-83. The long alkyl chains of the above-mentioned surfactants preferably have 10 to 18 carbon atoms. Esterquats are known substances which contain both at least one ester function and at least one quaternary ammonium group as a structural element. Preferred ester quats are quaternized ester salts of fatty acids with triethanolamine, quaternized ester salts of fatty acids with diethanolalkylamines and quaternized ester salts of fatty acids with 1,2-dihydroxypropyldialkylamines. Such products are marketed under the trade names Stepantex® ^®, ^® and Dehyquart® Armocare® ^®. The products Armocare ^® VGH-70, a N, N-bis (2-palmitoyloxyethyl) dimethylammonium chloride, as well as Dehyquart ^® F-75 and Dehyquart ^® AU-35 are examples of such esterquats.

The alkylamidoamines are usually prepared by amidation of natural or synthetic fatty acids and fatty acid cuts with dialkylaminoamines. An inventively particularly suitable compound from this group is that available under the name Tegoamid ^® S 18 commercially stearamidopropyl dimethylamine.

Further cationic surfactants which can be used according to the invention are the quaternized protein hydrolysates.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) and Abil ^® quat 3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary polydimethylsiloxanes, quaternium-80).

An example of a suitable cationic surfactant quaternary sugar derivative is the commercial product Glucquat ^® 100, according to INCI nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride".

The compounds used as surfactant with alkyl groups may each be uniform substances. However, it is generally preferred to use native vegetable or animal raw materials in the production of these substances, so that substance mixtures having different alkyl chain lengths depending on the respective raw material are obtained.

In the case of the surfactants which are adducts of ethylene oxide and / or propylene oxide with fatty alcohols or derivatives of these addition products, both products with a "normal" homolog distribution and those with a narrow homolog distribution can be used. Under "normal" homolog distribution are mixtures of Homologs obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Narrowed homolog distributions are obtained when, for example, hydrotalcites, alkaline earth metal salts of ether carboxylic acids, alkaline earth metal oxides, hydroxides or alkoxides are used as catalysts. The use of products with narrow homolog distribution may be preferred.

In addition, the cosmetic agents may contain further active ingredients, auxiliaries and additives, such as, for example, nonionic polymers such as, for example, vinylpyrrolidone / vinyl acrylate copolymers,

Polyvinylpyrrolidone and vinylpyrrolidone / vinyl acetate copolymers and polysiloxanes, cationic polymers such as quaternized cellulose ethers, polysiloxanes with quaternary

Groups, dimethyldiallylammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, diethyl sulfate quaternized dimethylaminoethylmethacrylate-vinylpyrrolidone copolymers, vinylpyrrolidone-imidazolinium methochloride copolymers and quaternized polyvinyl alcohol, zwitterionic and amphoteric polymers such as acrylamidopropyltrimidine methylammonium chloride / acrylate copolymers and octylacrylamide / methyl methacrylate / tert-butyl

Butylaminoethyl methacrylate, hydroxypropyl methacrylate copolymers, anionic polymers such as polyacrylic acids, crosslinked polyacrylic acids,

Vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl acrylate copolymers,

Vinyl acetate / butyl maleate / isobornyl acrylate copolymers, methyl vinyl ether / maleic anhydride

Copolymers and acrylic acid / ethyl acrylate / N-tert-butyl acrylamide terpolymers,

Structural agents such as maleic acid and lactic acid, hair conditioning compounds such as phospholipids, for example soya lecithin, egg lecithin and cephalins,

Protein hydrolysates, in particular elastin, collagen, keratin, milk protein, soy protein and

Wheat protein hydrolysates, their condensation products with fatty acids and quaternized

protein,

Perfume oils, dimethylisosorbide and cyclodextrins,

Solvents and mediators such as ethanol, isopropanol, ethylene glycol, propylene glycol, glycerol and diethylene glycol, fiber structure-improving agents, in particular mono-, di- and oligosaccharides such as glucose, galactose, fructose, fructose and lactose, quaternized amines such as methyl-1-alkylamidoethyl -2-alkylimidazolinium methosulfate

Defoamers like silicones,

Dyes for staining the agent,

Anti-dandruff agents such as Piroctone Olamine, Zinc Omadine and Climbazole, Light stabilizers, in particular derivatized benzophenones, cinnamic acid derivatives and

triazines,

Substances for adjusting the pH, such as conventional acids, in particular

Pleasure acids and bases,

Active ingredients such as allantoin, pyrrolidonecarboxylic acids and their salts, and bisabolol,

Vitamins, provitamins and vitamin precursors, in particular those of groups A, B ₃ , B ₅ , B ₆ ,

C, E, F and H,

Plant extracts such as extracts of green tea, oak bark, stinging nettle, witch hazel,

Hops, chamomile, burdock root, horsetail, hawthorn, lime blossom, almond, aloe vera,

Spruce needle, horse chestnut, sandalwood, juniper, coconut, mango, apricot, lime,

Wheat, kiwi, melon, orange, grapefruit, sage, rosemary, birch, mallow,

Meadowfoam, Quendel, Yarrow, Thyme, Melissa, Hauhechel, Coltsfoot, Marshmallow,

Meristem, ginseng and ginger root ,.

Cholesterol,

Bodying agents such as sugar esters, polyol esters or polyol alkyl ethers,

Fats and waxes such as spermaceti, beeswax, montan wax and paraffins,

fatty acid,

Complexing agents such as EDTA, NTA ₁ β-alaninediacetic acid and phosphonic acids,

Swelling and penetration substances such as glycerol, propylene glycol monoethyl ether, carbonates,

Hydrogencarbonates, guanidines, ureas and primary, secondary and tertiary phosphates,

Opacifiers such as latex, styrene / PVP and styrene / acrylamide copolymers

Pearlescing agents such as ethylene glycol mono- and distearate and PEG-3-distearate,

pigments

Stabilizing agent for hydrogen peroxide and other oxidizing agents,

Propellants such as propane-butane mixtures, N ₂ O, dimethyl ether, CO ₂ and air,

Antioxidants.

For the second subject of the invention applies mutatis mutandis what has been said for the first subject of the invention.

A third subject of the invention is a method for oxidative hair treatment, in which an oxidative cosmetic agent containing at least one oxidizing agent in a cosmetic carrier is applied to the hair and rinsed from the hair after a contact time at the same time as or immediately after the application of the oxidative cosmetic agent to the sites treated with the oxidative cosmetic agent, a cosmetic agent comprising, in a cosmetic carrier, an active ingredient (W) selected from at least one member of the group is made from compounds of formula (I)

wherein

R ¹ is a C ₂ to C ₁₂ acyl group and

R ² is a C ₂ to C ₃₀ alkyl group,

Theobroma cacao extract,

Compounds according to formula (II),

wherein

R ³ is a linear C ₁₂ - to C ₃₀ -alkyl group or a saturated or unsaturated ω-

(C ₁₂ - to C ₂₀₎ acyloxy (C ₂ -C ₃₀₎ alkyl group (such as preferably tricosanyl, Heptadecanyl or ω- (octadeca-9,12-dien-oyloxy) -nonacosanyl) and

R ⁴ is a saturated or unsaturated C ₁₅ -alkyl group or a saturated or unsaturated C ₁₅ -hydroxyalkyl group (such as, for example, pentadeca-1 -ene-1-yl, 3

Hydroxypentadeca-1 -ene-1-yl, 1-hydroxypentadecanyl), hydrolysed yeast extract, hydrolyzed lupine protein, in particular from Lupinus albus,

Rosemary extract,

Castanea sativa extract,

Mentha piperita leaf extract,

cholesterol, Compounds of the formula (III)

wherein

R ¹ , R ² and R ³ independently of one another represent a hydrogen atom, -CH ₃ , -CH ₂ CH ₃ ,

linoleic acid,

Vitamin C and derivatives thereof and niacinamide is applied and rinsed off again after an exposure time.

Particularly preferably, the oxidative cosmetic agent and the cosmetic agent are applied to the hair of the head.

The exposure time of the active ingredient (W) is preferably 1 to 100 minutes, more preferably 5 to 50 minutes.

Again, it is preferred according to the invention to use the method according to the invention in the context of an oxidative hair coloring, the oxidative hair bleaching or the fixation in the context of a permanent wave. It is preferred to apply the active ingredient (W) together with the oxidizing agent on the hair.

In a preferred embodiment of the method according to the invention as an oxidative hair dyeing method, the active ingredient (W) is preferably used as a constituent of a cosmetic agent additionally comprising at least one oxidizing agent and at least one oxidation dye precursor in one step in a cosmetic carrier. It is also preferred to use the active ingredient (W) immediately after rinsing the oxidative hair dye, for example in a conditioner.

The oxidative hair dyes of this embodiment are preferably two-component agents. The first component contains in a cosmetic carrier the active ingredient (W) and at least one oxidation dye precursor. The second component contains at least one oxidizing agent in a cosmetic carrier. These components are preferably packaged separately in each case in a compartment and provided together in a packaging unit (kit). In the embodiment of the method according to the invention as an oxidative hair bleaching method, the active ingredient (W) is preferably used as a constituent of a cosmetic agent additionally comprising at least one oxidizing agent and at least one bleaching booster in one step in a cosmetic carrier. It is also preferred to use the active ingredient (W) immediately after rinsing the oxidative hair dye, for example in a conditioner.

The means for carrying out the method according to the invention can be provided in a packaging unit. The packaging unit may contain at least either a container containing the agent of the second subject of the invention or containing at least two containers, the first container containing the oxidative cosmetic agent and the second container containing the cosmetic agent containing the active ingredient (W). The two Kontainer can also be as two chambers of a multi-chamber container.

For the third subject of the invention mutatis mutandis applies to the first and second subject of the invention.

The following examples are intended to illustrate the subject matter of the present invention without, however, limiting it.

B e i s p e e l e

The following formulations were provided using known preparation methods. The following commercial products were used as raw materials:

Niacinamide (INCI name: Niacinamide) SK-Influx ^® (INCI name: Ceramide I) (Degussa Care Specialties)

Merospheres ^® (INCI name: Rosmarinum Officinalis Extract, lecithin) (Barnet)

Structurine ^® (INCI name: Hydrolyzed Lupine Protein (Lupinus Albus) (Silab)

Calmosensine ^® acetyl Dipeptide-1 cetyl ester active substance: 1 wt .-%; (INCI name: Butylene Glycol, Aqua (Water), Laureth-3, Hydroxyethyl Cellulose, Acetyl Dipeptide-1 Cetyl Ester) (Sederma)

Caomint ^® (INCI name: Propylene Glycol, Aqua (Water), Mentha piperita (Peppermint) Leaf Extract, Theobroma Cacao (Cocoa) Extract) (Solabia)

Relipidum Ref ^® (INCI name: Hydrolyzed Yeast Extract, Butylene Glycol, methyl paraben) (Coletica) Hydrenol D ^® C ₆ -C ₁₈ fatty alcohol (INCI name: Cetearyl Alcohol) (Cognis Germany) Lorol ^® techn. C ₂ -C ₁₈ fatty alcohol (INCI name: Coconut alcohol) (Cognis Germany) Eumulgin ^® B1 Cetylstearylakohol with 12 EO units

(INCI name: Ceteareth-12) (Cognis Germany) Eumulgin B2 ^® cetylstearyl alcohol with about 20 EO units (INCI name: Ceteareth-20) (Cognis Germany) Turpinal SL ^® 1-hydroxyethane-1, 1-diphosphonic acid ( INCI name: Etidronic Acid, Aqua (Water)) (Solutia) Plantapon ^® LGC alkylpolyglucoside-carboxylate sodium salt; 30% active ingredient (Cognis Germany) Texapon ^® NSO sodium lauryl ether sulfate (27% active substance; INCI: Sodium Laureth Sulfate) (Cognis), Aculyn ^® 33 30 wt .-% of active substance in water (INCI name: Acrylates Copolymer) (Rohm & Haas ) DOW ^Corning® DB 110 A nonionic silicone emulsion (10% by weight of active substance) (INCI name: Dimethicone) (Dow Corning) 1.1 Coloring cream:

The quantities are wt .-% based on the total weight of the Colorationscreme.

1.2 developer emulsion:

One of the coloration creams and the developer emulsion were mixed in a weight ratio of 1: 1 and the mixture was applied to a subject on the head hair. After an exposure time of 45 minutes, the hair was rinsed and dried.

The colorations were carried out with each coloration cream according to the invention E1 to E8.

Claims

Patent claims

1. Cosmetic use of an agent comprising in a cosmetic carrier at least one active ingredient (W) selected from the group formed from - Compounds according to formula (I)

wherein

(C ₁₂ - to C ₂ o) -acyloxy- (C ₁₂ -C ₃₀ ) -alkyl group (as preferred tricosanyl, heptadecanyl or ω- (octadeca-9,12-dienyloxy) -nonacosanyl) and

R ⁴ is a saturated or unsaturated C ₁₅ -alkyl group or a saturated or unsaturated C ₁₅ -hydroxyalkyl group (such as, for example, pentadeca-1-en-1-yl, 3

Rosemary extract,

Castanea sativa extract,

Mentha piperita leaf extract,

cholesterol, Compounds of the formula (III)

wherein

-CH (CH ₃ ) ₂ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ J ₃ , n is 1 or 2,

- linoleic acid,

- Vitamin C and derivatives thereof and

- Niacinamide for skin soothing during or immediately after oxidative hair treatment.

2. Composition comprising, in a cosmetic carrier, a combination of at least one oxidizing agent and an active ingredient (W) selected from at least one member of the group which is formed from - Compounds according to formula (I)

wherein

R ¹ is a C ₂ to C ₁₂ acyl group and

R ² is a C ₂ to C ₃₀ alkyl group,

Theobroma cacao extract,

Compounds according to formula (II),

wherein R ³ is a linear C ₁₂ - to C ₃₀ -alkyl group or a saturated or unsaturated ω- (C ₁₂ - to C ₂₀ ) -acyloxy- (C ₁₂ -C ₃₀ ) -alkyl group (as preferred tricosanyl, heptadecanyl or ω- (Octadeca-9,12-dienyloxy) -nonacosanyl) and

R ⁴ represents a saturated or unsaturated C ₁₅ -alkyl group or a saturated or unsaturated C ₁₅ -hydroxyalkyl group (such as, for example, pentadeca-1-en-1-yl, 3-hydroxypentadeca-1-en-1-yl, 1-hydroxypentadecanyl) .

hydrolysed yeast extract,

hydrolyzed lupine protein, in particular from Lupinus albus,

- rosemary extract,

- Castanea sativa extract,

- Mentha piperita leaf extract,

- cholesterol,

Compounds of the formula (III),

- linoleic acid,

- Vitamin C and derivatives thereof and

- Niacinamide.

3. Composition according to claim 2, characterized in that it contains the active ingredient (W) in an amount of 0.01 to 7 wt .-%, based on the weight of the ready-to-use agent.

4. Composition according to one of claims 2 or 3, characterized in that it additionally contains at least one color-modifying component.

5. Composition according to claim 4, characterized in that the color-changing component is selected

(b) from oxo dye precursors and or

(c) from at least one direct dye and / or

(D) from at least one precursor of natural dyes and / or

(e) at least one bleach booster.

6. Composition according to one of claims 2 to 5, characterized in that it additionally contains at least one surfactant.

7. Composition according to one of claims 2 to 6, characterized in that the oxidizing agent is hydrogen peroxide and / or at least one addition product of hydrogen peroxide to inorganic or organic compounds.

8. Composition according to one of claims 2 to 7, characterized in that the oxidizing agent in an amount of 1, 0 to 10.0 wt .-% based on the weight of the ready-to-use agent, is included.

9. A method for oxidative hair treatment, in which an oxidative cosmetic agent, containing in a cosmetic carrier at least one oxidizing agent is applied to the hair and rinsed after an exposure time from the hair, simultaneously with or immediately after the application of the oxidative cosmetic agent on the bodies treated with the oxidative cosmetic agent, a cosmetic composition comprising, in a cosmetic vehicle, an active substance (W) selected from at least one member of the group which is formed from - compounds according to formula (I)

wherein

R ¹ is a C ₂ to C ₁₂ acyl group and R ² is a C ₂ to C ₃₀ alkyl group, Theobroma cacao extract, Compounds according to formula (II),

wherein

(C ₁₂ - to C ₂ o) acyloxy (C ₂ -C ₃₀₎ alkyl group (such as preferably tricosanyl, Heptadecanyl or ω- (octadeca-9,12-dien-oyloxy) -nonacosanyl) and

Rosemary extract,

Castanea sativa extract,

Mentha piperita leaf extract,

cholesterol,

Compounds of the formula (III)

wherein

-CH (CH ₃ J ₂ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) ₂ , -C (CH ₃ ) ₃ , n is 1 or 2,

- linoleic acid,

- Vitamin C and derivatives thereof and

- Niacinamide is applied and rinsed again after a contact time.